JP5631392B2 - Phenylphosphonate flame retardant composition - Google Patents

Description

  The present invention relates to a flame retardant polymer composition comprising phenylphosphonate in combination with a so-called sterically hindered nitroxyl derivative. The composition is particularly useful for the production of flame retardant compositions based on thermoplastic polymers, in particular polyolefin homo- and copolymers, and copolymers of vinyl monomers.

  A flame retardant is added to the polymer material (synthetic or natural) to enhance the flame retardancy of the polymer. Depending on their composition, flame retardants act on the solid phase, liquid phase or gas phase chemically, eg as a foaming agent by liberating nitrogen and / or physically, eg by creating a foam coating. be able to. Flame retardants interfere during certain stages of the combustion process, such as during heating, decomposition, ignition or fire spread.

  There remains a need for flame retardant compositions with improved properties that can be used on different polymer substrates. Increasing standards for safety and environmental requirements have led to stricter regulations. In particular, known halogen-containing flame retardants no longer meet all necessary requirements. Therefore, a halogen-free flame retardant is preferable from the viewpoint of a good function with respect to smoke concentration accompanied by fire. Improved thermal stability and low corrosion behavior are further advantages of halogen-free flame retardant compositions.

  Surprisingly, it has been found that excellent flame retardant polymers are prepared by the event of adding a phenylphosphonate in combination with a so-called sterically hindered amine to the polymer substrate. Furthermore, flame dripping is significantly reduced during the application of fire.

  Further advantages of the present invention are improved electrical properties (CTI = comparative tracking index) that cannot be achieved by using halogenated FR systems and low interaction with the polymer matrix during processing (reduced molecular weight reduction). ). In addition, the flame retardant is resistant to so-called leaching. Contact with water does not diminish these flame retardant activities.

  Surprisingly, it has been found that halogen-containing flame retardants such as decabromodiphenyl oxide, antimony compounds and fillers can be greatly reduced or replaced by the use of the flame retardant composition of the present invention.

のメラミンフェニルホスホン酸塩
及び
ｂ′）下記式：

のグアニジンフェニルホスホン酸塩
〔式中、
Ｒ₁〜Ｒ₅は、互いに独立して、水素又はＣ₁〜Ｃ₄アルキル、ヒドロキシ、ヒドロキシ−Ｃ₁〜Ｃ₄アルキル及びＣ₁〜Ｃ₄アルコキシからなる群より選択される置換基を表し；
Ｒ₆〜Ｒ₉は、互いに独立して、水素又はＣ₁〜Ｃ₄アルキル、フェニル、フェニル−Ｃ₁〜Ｃ₄アルキル、（Ｃ₁〜Ｃ₄アルキル）₁₋₃フェニル及び（Ｃ₁〜Ｃ₄アルキル）₁₋₂ヒドロキシフェニルからなる群より選択される置換基を表し；そして
ｘは、１．０〜２．０の数を表す〕
からなる群より選択されるフェニルホスホン酸塩と；
ｂ）２，２，６，６−テトラアルキルピペリジン−１−オキシド、１−ヒドロキシ−２，２，６，６−テトラアルキルピペリジン、１−アルコキシ−２，２，６，６−テトラアルキルピペリジン、１−アシルオキシ−２，２，６，６−テトラアルキルピペリジン、１−ヒドロキシ−２，２，６，６−テトラアルキルピペラジン、１−アルコキシ−２，２，６，６−テトラアルキルピペラジン及び１−アシルオキシ−２，２，６，６−テトラアルキルピペラジンからなる群より選択されるテトラアルキルピペリジン又はテトラアルキルピペラジン誘導体と；
ｃ）ポリマー基材と
を含む組成物、特に難燃性組成物に関する。 The present invention
a) The following:
a ′) the following formula:

Of melamine phenylphosphonate and b ′)

A guanidine phenylphosphonate salt of the formula
R _{1 to} R ₅ independently of one another represent hydrogen or a substituent selected from the group consisting of C ₁ -C ₄ alkyl, hydroxy, hydroxy-C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy;
R _{6 to} R ₉ are independently of each other hydrogen or C ₁ -C ₄ alkyl, phenyl, phenyl-C ₁ -C ₄ alkyl, (C ₁ -C ₄ alkyl) _1-3 phenyl and (C ₁ -C ₄ alkyl) represents a substituent selected from the group consisting of _1-2 hydroxyphenyl; and x represents a number from 1.0 to 2.0.
A phenylphosphonate selected from the group consisting of:
b) 2,2,6,6-tetraalkylpiperidine-1-oxide, 1-hydroxy-2,2,6,6-tetraalkylpiperidine, 1-alkoxy-2,2,6,6-tetraalkylpiperidine, 1-acyloxy-2,2,6,6 -tetraalkylpiperazine , 1-hydroxy-2,2,6,6-tetraalkylpiperazine, 1-alkoxy-2,2,6,6-tetraalkylpiperazine and 1- A tetraalkylpiperidine or tetraalkylpiperazine derivative selected from the group consisting of acyloxy-2,2,6,6- tetraalkylpiperazine ;
c) relates to a composition comprising a polymer substrate, in particular a flame retardant composition.

  The above-defined composition used as a flame retardant is another embodiment of the present invention.

A preferred embodiment of the present invention is:
a) The following:
a ') melamine phenylphosphonate (I) and b') guanidine phenylphosphonate (II)
〔here,
R _{1 to} R ₅ represent hydrogen; or 1 to 3 R _{1 to} R ₅ are selected from the group consisting of C _{1 to} C ₄ alkyl, hydroxy-C _{1 to} C ₄ alkyl and C _{1 to} C ₄ alkoxy The other substituents represent hydrogen;
R _{6 to} R ₉ independently of one another represent hydrogen or a substituent selected from the group consisting of C _{1 to} C ₄ alkyl and phenyl; and x represents a number from 1.0 to 2.0.
A phenylphosphonate selected from the group consisting of:
b) 2,2,6,6-tetraalkylpiperidine-1-oxide, 1-hydroxy-2,2,6,6-tetraalkylpiperidine, 1-alkoxy-2,2,6,6-tetraalkylpiperidine and A tetraalkylpiperidine derivative selected from the group consisting of 1-acyloxy-2,2,6,6- tetraalkylpiperidine ;
c) relates to a composition comprising a polymer substrate, in particular a flame retardant composition.

〔式中、ｘは、１．０〜２．０の数を表す〕のメラミンフェニルホスホン酸塩；及び
ｂ′）下記式：

〔式中、ｘは、１．０〜２．０の数を表す〕のグアニジンフェニルホスホン酸塩
からなる群より選択されるフェニルホスホン酸塩と；
ｂ）２，２，６，６−テトラアルキルピペリジン−１−オキシド、１−ヒドロキシ−２，２，６，６−テトラアルキルピペリジン、１−アルコキシ−２，２，６，６−テトラアルキルピペリジン及び１−アシルオキシ−２，２，６，６−テトラアルキルピペリジンからなる群より選択されるテトラアルキルピペリジン誘導体と；
ｃ）ポリマー基材と
を含む組成物、特に難燃性組成物に関する。 A more preferred embodiment of the present invention is:
a) The following:
a ′) the following formula:

Wherein x represents a number from 1.0 to 2.0; and b ') the following formula:

A phenylphosphonate selected from the group consisting of guanidine phenylphosphonates, wherein x represents a number from 1.0 to 2.0;
b) 2,2,6,6-tetraalkylpiperidine-1-oxide, 1-hydroxy-2,2,6,6-tetraalkylpiperidine, 1-alkoxy-2,2,6,6-tetraalkylpiperidine and A tetraalkylpiperidine derivative selected from the group consisting of 1-acyloxy-2,2,6,6- tetraalkylpiperidine ;
c) relates to a composition comprising a polymer substrate, in particular a flame retardant composition.

Particularly preferred embodiments of the present invention are:
a) phenylphosphonate (I ′) or (II ′);
b) a tetraalkylpiperidine derivative selected from the group consisting of 1-alkoxy-2,2,6,6-tetraalkylpiperidine and 1-acyloxy-2,2,6,6- tetraalkylpiperidine ;
c) relates to a composition comprising a polymer substrate.

  The composition of the present invention exhibits excellent flame retardancy. Depending on the concentration of components a) and b) in the polymer substrate, V-0 or V-2 ranking according to UL-94 (Underwriters Laboratories Subject 94) and other superior ranks in related test methods I'm getting attached.

Particularly preferred embodiments of the present invention are:
a) phenylphosphonate (I ′) or (II ′);
b) a tetraalkylpiperidine derivative selected from the group consisting of 1-alkoxy-2,2,6,6-tetraalkylpiperidine and 1-acyloxy-2,2,6,6- tetraalkylpiperidine ;
c) relates to a composition comprising a thermoplastic polymer.

  The composition as defined above comprises the following components:

のメラミンフェニルホスホン酸塩において、
Ｒ₁〜Ｒ₅は、互いに独立して、水素又はＣ₁〜Ｃ₄アルキル、例えばメチル、エチル、ｎ−、イソプロピル又はｎ−、イソ−若しくはｔｅｒｔ−ブチル、ヒドロキシ、ヒドロキシ−Ｃ₁〜Ｃ₄アルキル、例えばヒドロキシメチル又は１−若しくは２−ヒドロキシエチル及びＣ₁〜Ｃ₄アルコキシ、例えばメトキシ又はエトキシからなる群より選択される置換基を表し、そしてｘは、１．０〜２．０の数を表す。 Ingredient a)
Following formula:

In the melamine phenylphosphonate of
R _{1 to} R ₅ are, independently of one another, hydrogen or C _{1 to} C ₄ alkyl, such as methyl, ethyl, n-, isopropyl or n-, iso- or tert-butyl, hydroxy, hydroxy-C ₁ -C ₄ alkyl, such as hydroxymethyl or 1- or 2-hydroxyethyl and C ₁ -C ₄ alkoxy, for example, represents a substituent selected from the group consisting of methoxy or ethoxy, and x is the number of 1.0 to 2.0 Represents.

のグアニジンフェニルホスホン酸塩において、
Ｒ₁〜Ｒ₅は、フェニルホスホン酸塩（Ｉ）に関して上記に定義されたとおりであり；
Ｒ₆〜Ｒ₉は、互いに独立して、水素又はＣ₁〜Ｃ₄アルキル、フェニル、フェニル−Ｃ₁〜Ｃ₄アルキル、例えばベンジル又は１−若しくは２−フェネチル、（Ｃ₁〜Ｃ₄アルキル）₁₋₃フェニル、例えばトリル又はメシチル及び（Ｃ₁〜Ｃ₄アルキル）₁₋₂ヒドロキシフェニル、例えば４−ヒドロキシ−３，５−ジ−ｔｅｒｔ−ブチルフェニル又は３−ｔｅｒｔ−ブチル−４−ヒドロキシ−５−メチルフェニルからなる群より選択される置換基を表し、そしてｘは、１．０〜２．０の数を表す。 Following formula:

In guanidine phenylphosphonate of
R _{1 to} R ₅ are as defined above for phenylphosphonate (I);
R _{6 to} R ₉ are, independently of one another, hydrogen or C ₁ -C ₄ alkyl, phenyl, phenyl-C ₁ -C ₄ alkyl, such as benzyl or 1- or 2-phenethyl, (C ₁ -C ₄ alkyl) _1-3 phenyl, for example tolyl or mesityl, and (C ₁ -C ₄ alkyl) _{1-2-hydroxyphenyl,} such as 4-hydroxy-3,5-di -tert- butylphenyl or 3-tert-butyl-4-hydroxy - Represents a substituent selected from the group consisting of 5-methylphenyl, and x represents a number from 1.0 to 2.0.

  Melamine phenylphosphonate (I) and guanidine phenylphosphonate (II) as defined above are known compounds and are described in US Pat. No. 4,061,605 (melamine phenylphosphonate (I)) and U.S. Pat. No. 4,308,197 (guanidine phenylphosphonate (II)).

  The composition of the present invention contains melamine phenylphosphonate (I) and guanidine phenylphosphonate (II) as separate components or as a mixture or combination of both.

〔式中、Ｒ₁〜Ｒ₅は上記に定義されたとおりである〕のフェニルホスホン酸と、
下記式：

〔式中、Ｒ₆〜Ｒ₉は上記に定義されたとおりである〕のメラミン若しくはグアニジン誘導体又はこれらの塩、例えば炭酸塩の、ｘ個の対応する当量での酸塩基反応により得られる。 These compounds can be obtained by known methods, for example:

A phenylphosphonic acid of the formula wherein R _{1 to} R ₅ are as defined above;
Following formula:

It is obtained by an acid-base reaction of melamine or guanidine derivatives of the formula, wherein R _{6 to} R ₉ are as defined above, or a salt thereof such as a carbonate with x corresponding equivalents.

  According to a preferred embodiment, melamine and guanidine phenylphosphonate are added from melamine carbonate or guanidine and phenylphosphonate, for example by adding both components as a hot aqueous solution followed by crystallization, filtration, drying and milling. Manufactured by.

のメラミンフェニルホスホン酸塩及び下記式：

のグアニジンフェニルホスホン酸塩が存在する組成物、特に難燃性組成物に関する。 A particularly preferred embodiment of the present invention has the following formula:

Melamine phenylphosphonate and the following formula:

Of guanidine phenylphosphonates, in particular flame retardant compositions.

  In the melamine phenylphosphonate (I) and guanidine phenylphosphonate (II) defined above, the molar ratio of phenylphosphonic acid and melamine or guanidine base is that x is 1.0 to 2.0. Correspondingly, it is 1: 1 to 2: 1.

  Component a) is added to the flame retardant composition of the present invention in an amount of 0.1 to 45.0% by weight, preferably 0.1 to 30.0% by weight, based on the weight of polymer substrate component c). Preferably contained, component b) is preferably contained in an amount of 0.05% to 5.0% by weight, preferably 0.1 to 2.0% by weight. Preferred ratios of components a): b) are in the range of 50: 1 to 1: 5, preferably 20: 1 to 1: 2.

Component b)
Suitable tetraalkylpiperidine or tetraalkylpiperazine derivatives are 2,2,6,6-tetraalkylpiperidine-1-oxide, 1-hydroxy-2,2,6,6-tetraalkylpiperidine, 1-alkoxy-2, 2,6,6-tetraalkylpiperidine, 1-acyloxy-2,2,6,6 -tetraalkylpiperidine , 1-hydroxy-2,2,6,6-tetraalkylpiperazine, 1-alkoxy-2,2, It is selected from the group consisting of 6,6-tetraalkylpiperazine and 1-acyloxy-2,2,6,6- tetraalkylpiperazine .

〔式中、Ｒ₁〜Ｒ₄は、Ｃ₁〜Ｃ₄アルキル、好ましくはメチル又はエチルを表す〕により例示することができる。好ましい実施態様によると、Ｒ₁とＲ₂の一方及びＲ₃とＲ₄の一方は、エチルを表し、他方はメチルを表すか又はＲ₁〜Ｒ₄の全ては、メチルを表し、そして
Ｅは、水素、Ｃ₁〜Ｃ₂₀アルキル、Ｃ₅〜Ｃ₆シクロアルキル又は追加の置換基を有するＣ₂〜Ｃ₂₀アルキル、Ｃ₅〜Ｃ₆シクロアルキル若しくはＣ₂〜Ｃ₂₀アルケニルを表すか；又はＣ₁〜Ｃ₂₀モノカルボン酸若しくはＣ₂〜Ｃ₂₀ジカルボン酸のアシル基を表す。 Such compounds have the following partial formula:

[Wherein R _{1 to} R ₄ represent C _{1 to} C ₄ alkyl, preferably methyl or ethyl]. According to a preferred embodiment, _one of R ₁ and R ₂ and one of R ₃ and R ₄ represents ethyl and the other represents methyl or all of R _{1 to} R ₄ represent methyl and E is , hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkyl having a C ₅ -C ₆ cycloalkyl or additional substituents, or represents C ₅ -C ₆ cycloalkyl or C ₂ -C ₂₀ alkenyl; or C ₁ -C represents a ₂₀ monocarboxylic acid or C ₂ -C ₂₀ acyl group of a dicarboxylic acid.

  In the compound corresponding to the partial formula a, one of the dotted lines at the 4-position of piperidine represents a bond to hydrogen or an N substituent, and the other represents a bond to an O substituent or a C substituent.

  Alternatively, both dotted lines at the 4-position of piperidine represent a bond to hydrogen, an O substituent or a C substituent, or represent a double bond to oxygen.

  In the compound corresponding to partial formula b, the nitrogen at the 4-position of piperazine is bonded to hydrogen or a carbon substituent.

A typical structural formula is presented below:

In these compounds (A) to (S),
Or E is hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkyl having a C ₅ -C ₆ cycloalkyl or additional substituents, represents a C ₅ -C ₆ cycloalkyl or C ₂ -C ₂₀ alkenyl Or an acyl group of C ₁ -C ₂₀ monocarboxylic acid or C ₂ -C ₂₀ dicarboxylic acid, or the group> N-O-E is replaced by the group> N-O.

  Alkyl is straight or branched chain, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n -Decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

  Cycloalkyl groups include cyclopentyl and cyclohexyl, typical cycloalkenyl groups include cyclohexenyl, but typical aralkyl groups include benzyl, α-methyl-benzyl, α, α-dimethyl. Benzyl or phenethyl are included.

E is defined as the acyl group of C ₁ -C ₂₀ monocarboxylic acids, preferably, -C (= O) -H, -C (= O) -C 1 ~C 19 alkyl, -C (= O) -C ₂ -C _{19 alkenyl, -C (= O) -C 2} ~C 4 alkenyl -C ₆ -C _{10 aryl, -C (= O) -C 6} ~C 10 aryl, -C (= O) - O-C ₁ ~C ₆ alkyl, -C (= O) -O- C 6 ~C 10 aryl, -C (= O) -NH- C 1 ~C 6 alkyl, -C (= O) -NH- An acyl group selected from the group consisting of C ₆ -C ₁₀ aryl and —C (═O) —N (C ₁ -C ₆ alkyl) ₂ .

E is defined as an acyl group of C ₂ -C ₂₀ dicarboxylic acids, for example, C group and diacyl group derived from a monobasic organic acid having two acid functional groups, such as aliphatic, aromatic or cycloaliphatic It is a diacyl group derived from a dicarboxylic acid.

  Suitable aliphatic dicarboxylic acids have 2 to 40 C atoms such as oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, pimelic acid, adipic acid, trimethyladipic acid, sebacic acid, azelaic acid, di-acid. A dimerization product (a dimerization product of an unsaturated aliphatic carboxylic acid such as oleic acid), an alkylated malonic acid and a succinic acid, such as octadecyl succinic acid.

  Suitable alicyclic dicarboxylic acids are, for example, 1,3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,3- and 1,4-cyclohexanedicarboxylic acid, 1,3- and 1,4- (Dicarboxymethyl) cyclohexane or 4,4'-dicyclohexyldicarboxylic acid.

  Preferred members of this group include oxalic acid, adipic acid, succinic acid, suberic acid, sebacic acid, phthalic acid, dibutylmalonic acid, dibenzylmalonic acid or butyl- (3,5-di-tert-butyl-4- Hydroxybenzyl) -malonic acid or bicycloheptene dicarboxylic acid acyl groups are included, succinate, sebacate, phthalate and isophthalate are specific examples.

When E is a divalent acyl group of dicarbamic acid, for example, an acyl group of hexamethylene dicarbamic acid or 2,4-toluylene dicarbamic acid;
T is linear or branched alkylene having 1 to 18 carbon atoms, cycloalkylene having 5 to 18 carbon atoms, cycloalkenylene having 5 to 18 carbon atoms, linear or branched alkylene having 1 to 4 carbon atoms Substituted by phenyl or phenyl substituted by 1 or 2 alkyl groups of 1 to 4 C atoms;
b is 1, 2 or 3 as long as b does not exceed the number of C atoms in T; when b is 2 or 3, each hydroxy group is bonded to a different C atom in T;
R is hydrogen or methyl; and m is 1-4.

〔式中、ｘは、０又は１である〕、

〔式中、ｙは２〜４である〕
の基を表し；
ｍが２の場合、
Ｒ₂は、Ｃ₁〜Ｃ₁₂アルキレン、Ｃ₄〜Ｃ₁₂アルケニレン、キシリレン、脂肪族、脂環式、芳香脂肪族若しくは芳香族ジカルボン酸の又はジカルバミン酸の二価アシル基、例えば、２〜１８個のＣ原子を有する脂肪族ジカルボン酸の、８〜１４個のＣ原子を有する脂環式若しくは芳香族ジカルボン酸の又は８〜１４個のＣ原子を有する脂肪族、脂環式若しくは芳香族ジカルバミン酸のアシル基であるか；或いは
下記の部分式：

〔式中、
Ｄ₁及びＤ₂は、独立して、水素か、３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル基を含むＣ₁〜Ｃ₈アルキル、アリール又はアラルキルであり、
Ｄ₃は、水素、Ｃ₁〜Ｃ₁₈アルキル又はＣ₁〜Ｃ₂₀アルケニルであり、そして
ｄは、０〜２０である〕
の基を表し；
ｍが３の場合、
Ｒ₂は、脂肪族、不飽和脂肪族、脂環式又は芳香族トリカルボン酸の三価アシル基であり；
ｍが４の場合、
Ｒ₂は、１，２，３，４−ブタンテトラカルボン酸、１，２，３，４−ブタ−２−エンテトラカルボン酸、１，２，３，５−及び１，２，４，５−ペンタンテトラカルボン酸を含む、飽和又は不飽和の脂肪族又は芳香族テトラカルボン酸の三価アシル基であり；
上記に記述された化合物において、変数ｐが１、２又は３の場合、
Ｒ₃は、水素、Ｃ₁〜Ｃ₁₂アルキル、Ｃ₅〜Ｃ₇シクロアルキル、Ｃ₇〜Ｃ₉アラルキル、Ｃ₂〜Ｃ₁₈アルカノイル、Ｃ₃〜Ｃ₅アルケノイル又はベンゾイルであり；
ｐが１の場合、
Ｒ₄は、水素、Ｃ₁〜Ｃ₁₈アルキル、Ｃ₅〜Ｃ₇シクロアルキル、Ｃ₂〜Ｃ₈アルケニル（非置換であるか又はシアノ、カルボニル若しくはカルバミドで置換されている）又はアリール、アラルキル若しくはグリシジルか、部分式：−ＣＨ₂−ＣＨ（ＯＨ）−Ｚの又は他の部分式：−ＣＯ−Ｚ若しくは−ＣＯＮＨ−Ｚの基（ここで、Ｚは、水素、メチル又はフェニルである）であるか；又は下記の部分式：

〔式中、ｈは、０又は１である〕
の基を表し；
Ｒ₃及びＲ₄は、ｐが１の場合、一緒になって、Ｃ原子４〜６個のアルキレン又は２−オキソ−ポリアルキレン又は脂肪族若しくは芳香族の１，２−若しくは１，３−ジカルボン酸の環状アシル基を表し；
ｐが２の場合、
Ｒ₄は、直接結合であるか又はＣ₁〜Ｃ₁₂アルキレン、Ｃ₆〜Ｃ₁₂アリーレン、キシリレン、−ＣＨ₂ＣＨ（ＯＨ）−ＣＨ₂−基若しくは部分式：−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−Ｏ−Ｘ−Ｏ−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−（ここでＸは、Ｃ₂〜Ｃ₁₀アルキレン、Ｃ₆〜Ｃ₁₅アリーレン又はＣ₆〜Ｃ₁₂シクロアルキレンである）の基であるか；或いはＲ₃が、アルカノイル、アルケノイル又はベンゾイル以外であれば、Ｒ₄は、脂肪族、脂環式若しくは芳香族のジカルボン酸又はジカルバミン酸の二価アシル基を追加的に表すか又は基−ＣＯ−を表すか；或いは
Ｒ₄は、下記の部分式：

〔式中、Ｔ₈及びＴ₉は、独立して、水素、Ｃ₁〜Ｃ₁₈アルキルであるか又はＴ₈及びＴ₉は、一緒になって、Ｃ₄〜Ｃ₈アルキレン若しくは３−オキサペンタメチレンを表し、例えばＴ₈及びＴ₉は、一緒になって、３−オキサペンタメチレンである〕
の基を表し；
ｐが３の場合、
Ｒ₄は、２，４，６−トリアジニルであり；
ｎは、１又は２であり；
ｎが１の場合、
Ｒ₅及びＲ′₅は、独立して、Ｃ₁〜Ｃ₁₂アルキル、Ｃ₂〜Ｃ₁₂アルケニル、Ｃ₇〜Ｃ₁₂アラルキルであるか又はＲ₅は追加的に水素を表すか、或いはＲ₅及びＲ′₅は、一緒になって、Ｃ₂〜Ｃ₈アルキレン又はヒドロキシアルキレン又はＣ₄〜Ｃ₂₄アシルオキシアルキレンであり；
ｎが２の場合、
Ｒ₅及びＲ′₅は、一緒になって、部分式；（−ＣＨ₂）₂Ｃ（ＣＨ₂−）₂の基であり；
Ｒ₆は、水素、Ｃ₁〜Ｃ₁₂アルキル、アリル、ベンジル、グリシジル又はＣ₂〜Ｃ₆アルコキシアルキルであるか；或いは
ｎが１の場合、
Ｒ₇は、水素、Ｃ₁〜Ｃ₁₂アルキル、Ｃ₃〜Ｃ₅アルケニル、Ｃ₇〜Ｃ₉アラルキル、Ｃ₅〜Ｃ₇シクロアルキル、Ｃ₂〜Ｃ₄ヒドロキシアルキル、Ｃ₂〜Ｃ₆アルコキシアルキル、Ｃ₆〜Ｃ₁₀アリール、グリシジル、式：−（ＣＨ₂）_t−ＣＯＯ−Ｑの若しくは部分式：−（ＣＨ₂）_t−Ｏ−ＣＯ−Ｑ（式中、ｔは、１若しくは２であり、そしてＱは、Ｃ₁〜Ｃ₄アルキル若しくはフェニルである）の基であるか；又は
ｎが２の場合、
Ｒ₇は、Ｃ₂〜Ｃ₁₂アルキレン、Ｃ₆〜Ｃ₁₂アリーレン、下記の部分式：
−ＣＨ₂ＣＨ（ＯＨ）−ＣＨ₂−Ｏ−Ｘ−Ｏ−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−
の基であり、
ここでＸは、Ｃ₂〜Ｃ₁₀アルキレン、Ｃ₆〜Ｃ₁₅アリーレン若しくはＣ₆〜Ｃ₁₂シクロアルキレン又は下記の部分式：
−ＣＨ₂ＣＨ（ＯＺ′）ＣＨ₂−（ＯＣＨ₂−ＣＨ（ＯＺ′）ＣＨ₂）₂−
の基であり、
ここでＺ′は、水素、Ｃ₁〜Ｃ₁₈アルキル、アリル、ベンジル、Ｃ₂〜Ｃ₁₂アルカノイル又はベンゾイルであり；
Ｑ₁は、−Ｎ（Ｒ₈）−又は−Ｏ−であり；Ｅ₇は、Ｃ₁〜Ｃ₃アルキレン、基−ＣＨ₂−ＣＨ（Ｒ₉）−Ｏ−（ここでＲ₉は、水素、メチル又はフェニルである）、基−（ＣＨ₂）₃−ＮＨ−又は直接結合であり；
Ｒ₁₀は、水素又はＣ₁〜Ｃ₁₈アルキルであり、Ｒ₈は、水素、Ｃ₁〜Ｃ₁₈アルキル、Ｃ₅〜Ｃ₇シクロアルキル，Ｃ₇〜Ｃ₁₂アラルキル、シアノエチル、Ｃ₆〜Ｃ₁₀アリール、基−ＣＨ₂−ＣＨ（Ｒ₉）−ＯＨ（ここでＲ₉は、上記で定義された意味を有する）であるか又は下記の部分式：

の基を表し、
ここでＧ₄は、Ｃ₂〜Ｃ₆アルキレン又はＣ₆〜Ｃ₁₂アリーレンであるか；或いはＲ₈は、部分式：−Ｅ₇−ＣＯ−ＮＨ−ＣＨ₂−ＯＲ₁₀の基であり；
式Ｆは、Ｔ₃がエチレン又は１，２−プロピレンであるポリマーの反復構造単位を示し、アルキルアクリレート又はアルキルメタクリレートとのα−オレフィンコポリマーから誘導される反復構造単位であり、例えばエチレンとエチルアクリレートのコポリマーであり、ここでｋは、２〜１００であり；
Ｔ₄は、ｐが１又は２の場合のＲ₄と同じ意味を有し；
Ｔ₅は、メチルであり；
Ｔ₆は、メチル又はエチルであるか、或いはＴ₅及びＴ₆は、一緒になって、テトラメチレン又はペンタメチレンであり、例えば、Ｔ₅及びＴ₆は、それぞれメチルであり；
Ｍ及びＹは、独立して、メチレン又はカルボニルであり、Ｔ₄は、ｎが２の場合、エチレンであり；
Ｔ₇は、Ｒ₇と同じように定義され、Ｔ₇は、ｎが２の場合、例えばオクタメチレンであり；
Ｔ₁₀及びＴ₁₁は、独立して、Ｃ原子２〜１２個のアルキレンであるか又はＴ₁₁は、下記の部分式：

の基を表し；
Ｔ₁₂は、ピペラジニル又は下記の部分式：

〔式中、Ｒ₁₁は、Ｒ₃と同じように定義されるか又は下記の部分式：

の基を追加的に表し、
ａ、ｂ及びｃは、独立して、２又は３であり、そしてｆは、０又は１であり、例えばａ及びｃは、それぞれ３であり、ｂは２であり、ｆは１である〕の基を表し；
ｅは、２，３又は４、例えば４であり；
Ｔ₁₃は、Ｒ₂と同じであるが、但しｎが１の場合、Ｔ₁₃は水素以外であり；
Ｅ₁及びＥ₂は、異なって、それぞれ−ＣＯ−又は−Ｎ（Ｅ₅）−であり、ここでＥ₅は、水素、Ｃ₁〜Ｃ₁₂アルキル又はＣ₄〜Ｃ₂₄アルコキシカルボニルアルキルであり、例えばＥ₁は−ＣＯ−であり、Ｅ₂は−Ｎ（Ｅ₅）−であり；
Ｅ₃は、水素、Ｃ₁〜Ｃ₃₀アルキル、フェニル、ナフチル、塩素若しくはＣ₁〜Ｃ₄アルキルで置換されている前記フェニル若しくは前記ナフチル、Ｃ₇〜Ｃ₁₂フェニルアルキル又はＣ₁〜Ｃ₄アルキルで置換されている前記フェニルアルキルであり；
Ｅ₄は、水素、Ｃ原子１〜３０個のアルキル、フェニル、ナフチル又はＣ原子７〜１２個のフェニルアルキルであるか、或いは
Ｅ₃及びＥ₄は、一緒になって、Ｃ原子４〜１７個のポリメチレン又はＣ₁〜Ｃ₄個のアルキルの４つまでにより置換されている前記ポリメチレン、例えばメチルであり；
Ｅ₆は、脂肪族又は芳香族四価基であり；
式（Ｎ）のＲ₂は、ｍが１の場合ですでに定義されており；
Ｇ₁は、直接結合、Ｃ₁〜Ｃ₁₂アルキレン、フェニレン又は−ＮＨ−Ｇ′−ＮＨであり、ここでＧ′は、Ｃ₁〜Ｃ₁₂アルキレンである。 In the compound described above, when the variable m is 1,
R ₂ is hydrogen, C ₁ -C ₁₈ alkyl, or said alkyl optionally interrupted with one or more oxygen atoms, C ₂ -C ₁₂ alkenyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₈ aralkyl, Glycidyl, aliphatic, cycloaliphatic or aromatic carboxylic acids or monovalent acyl groups of carbamic acid, for example aliphatic carboxylic acids having 2 to 18 C atoms, fats having 5 to 12 C atoms Is an acyl group of a cyclic carboxylic acid or of an aromatic carboxylic acid having 7 to 15 C atoms, or the following partial formula:

[Wherein x is 0 or 1],

[Wherein y is 2 to 4]
Represents a group of
If m is 2,
R ₂ is a C ₁ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, xylylene, aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid or dicarbamic acid divalent acyl group, for example 2-18 Of aliphatic dicarboxylic acids having 8 C atoms, alicyclic or aromatic dicarboxylic acids having 8 to 14 C atoms, or aliphatic, alicyclic or aromatic dicarbamines having 8 to 14 C atoms The acyl group of the acid; or

[Where,
D ₁ and D ₂ are independently hydrogen or C ₁ -C ₈ alkyl, aryl or aralkyl containing a 3,5-di-tert-butyl-4-hydroxybenzyl group;
D ₃ is hydrogen, C ₁ -C ₁₈ alkyl or C ₁ -C ₂₀ alkenyl, and d is 0-20]
Represents a group of
If m is 3,
R ₂ is a trivalent acyl group of an aliphatic, unsaturated aliphatic, alicyclic or aromatic tricarboxylic acid;
If m is 4,
R ₂ is 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-but-2-enetetracarboxylic acid, 1,2,3,5- and 1,2,4,5 A trivalent acyl group of a saturated or unsaturated aliphatic or aromatic tetracarboxylic acid, including pentanetetracarboxylic acid;
In the compounds described above, when the variable p is 1, 2 or 3,
R ₃ is hydrogen, C ₁ -C ₁₂ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₉ aralkyl, C ₂ -C ₁₈ alkanoyl, C ₃ -C ₅ alkenoyl or benzoyl;
If p is 1,
R ₄ is hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₇ cycloalkyl, C ₂ -C ₈ alkenyl (unsubstituted or substituted with cyano, carbonyl or carbamide) or aryl, aralkyl or Glycidyl or a group of the partial formula: —CH ₂ —CH (OH) —Z or other partial formula: —CO—Z or —CONH—Z, where Z is hydrogen, methyl or phenyl. Or the following sub-formula:

[Wherein h is 0 or 1]
Represents a group of
R ₃ and R ₄ , when p is 1, together are alkylene of 4 to 6 C atoms or 2-oxo-polyalkylene or aliphatic or aromatic 1,2- or 1,3-dicarboxylic Represents a cyclic acyl group of an acid;
If p is 2,
R ₄ is a direct bond, or C ₁ -C ₁₂ alkylene, C ₆ -C ₁₂ arylene, xylylene, —CH ₂ CH (OH) —CH ₂ — group or partial formula: —CH ₂ —CH (OH) —CH ₂ —O—X—O—CH ₂ —CH (OH) —CH ₂ —, where X is C ₂ -C ₁₀ alkylene, C ₆ -C ₁₅ arylene or C ₆ -C ₁₂ cycloalkylene. Or if R ₃ is other than alkanoyl, alkenoyl or benzoyl, R ₄ additionally represents a divalent acyl group of an aliphatic, alicyclic or aromatic dicarboxylic acid or dicarbamic acid. Or represents the group —CO—; or R ₄ represents the following partial formula:

[Wherein T ₈ and T ₉ are independently hydrogen, C ₁ -C ₁₈ alkyl, or T ₈ and T ₉ are taken together to form C ₄ -C ₈ alkylene or 3-oxapenta Represents methylene, for example, T ₈ and T ₉ together are 3-oxapentamethylene]
Represents a group of
If p is 3,
R ₄ is 2,4,6-triazinyl;
n is 1 or 2;
When n is 1,
R ₅ and R ′ ₅ are independently C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₇ -C ₁₂ aralkyl, or R ₅ additionally represents hydrogen, or R ₅ And R ′ ₅ together are C ₂ -C ₈ alkylene or hydroxyalkylene or C ₄ -C ₂₄ acyloxyalkylene;
When n is 2,
R ₅ and R ′ ₅ together are a group of the partial formula; (—CH ₂ ) ₂ C (CH ₂ —) ₂ ;
R ₆ is hydrogen, C ₁ -C ₁₂ alkyl, allyl, benzyl, glycidyl or C ₂ -C ₆ alkoxyalkyl; or when n is 1,
R ₇ is hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₅ alkenyl, C ₇ -C ₉ aralkyl, C ₅ -C ₇ cycloalkyl, C ₂ -C ₄ hydroxyalkyl, C ₂ -C ₆ alkoxyalkyl , C ₆ -C ₁₀ aryl, glycidyl, formula: — (CH ₂ ) _t —COO—Q or partial formula: — (CH ₂ ) _t —O—CO—Q wherein t is 1 or 2 And Q is C ₁ -C ₄ alkyl or phenyl); or when n is 2,
R ₇ is C ₂ -C ₁₂ alkylene, C ₆ -C ₁₂ arylene, the following partial formula:
—CH ₂ CH (OH) —CH ₂ —O—X—O—CH ₂ —CH (OH) —CH ₂ —
The basis of
Where X is C ₂ -C ₁₀ alkylene, C ₆ -C ₁₅ arylene or C ₆ -C ₁₂ cycloalkylene or the following partial formula:
_{-CH 2 CH (OZ ') CH} 2 - (OCH 2 -CH (OZ') CH 2) 2 -
The basis of
Where Z ′ is hydrogen, C ₁ -C ₁₈ alkyl, allyl, benzyl, C ₂ -C ₁₂ alkanoyl or benzoyl;
Q ₁ is —N (R ₈ ) — or —O—; E ₇ is C ₁ -C ₃ alkylene, the group —CH ₂ —CH (R ₉ ) —O—, where R ₉ is hydrogen. , Methyl or phenyl), a group — (CH ₂ ) ₃ —NH— or a direct bond;
R ₁₀ is hydrogen or C ₁ -C ₁₈ alkyl, R ₈ is hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₁₂ aralkyl, cyanoethyl, C ₆ -C ₁₀ An aryl, group —CH ₂ —CH (R ₉ ) —OH, where R ₉ has the meaning defined above, or the following sub-formula:

Represents the group of
Where G ₄ is C ₂ -C ₆ alkylene or C ₆ -C ₁₂ arylene; or R ₈ is a group of the partial formula: —E ₇ —CO—NH—CH ₂ —OR ₁₀ ;
Formula F represents a repeating structural unit of a polymer in which T ₃ is ethylene or 1,2-propylene, and is a repeating structural unit derived from an α-olefin copolymer with an alkyl acrylate or alkyl methacrylate, such as ethylene and ethyl acrylate. Wherein k is 2 to 100;
T ₄ has the same meaning as R ₄ when p is 1 or 2;
T ₅ is methyl;
T ₆ is methyl or ethyl, or T ₅ and T _{6 taken} together are tetramethylene or pentamethylene, for example, T ₅ and T ₆ are each methyl;
M and Y are independently methylene or carbonyl, and T ₄ is ethylene when n is 2,
T ₇ is defined the same as R ₇ , where T ₇ is, for example, octamethylene when n is 2;
T ₁₀ and T ₁₁ are independently an alkylene of 2 to 12 C atoms, or T ₁₁ is the following sub-formula:

Represents a group of
T ₁₂ is piperazinyl or the following partial formula:

[Wherein R ₁₁ is defined in the same manner as R ₃ or the following sub-formula:

Additional groups of
a, b, and c are independently 2 or 3, and f is 0 or 1, for example, a and c are each 3, b is 2, and f is 1. Represents a group of
e is 2, 3 or 4, eg 4;
T ₁₃ is the same as R ₂ except that when n is 1, T ₁₃ is other than hydrogen;
E ₁ and E ₂ are different and are each —CO— or —N (E ₅ ) —, where E ₅ is hydrogen, C ₁ -C ₁₂ alkyl or C ₄ -C ₂₄ alkoxycarbonylalkyl. For example, E ₁ is —CO— and E ₂ is —N (E ₅ ) —;
E ₃ is hydrogen, C ₁ -C ₃₀ alkyl, phenyl, naphthyl, chlorine or the above phenyl or naphthyl substituted with C ₁ -C ₄ alkyl, C ₇ -C ₁₂ phenyl alkyl or C ₁ -C ₄ alkyl Said phenylalkyl substituted with
E ₄ is hydrogen, alkyl having 1 to 30 carbon atoms, phenyl, naphthyl, or phenylalkyl having 7 to 12 carbon atoms, or E ₃ and E ₄ together can form _{4 to} 17 carbon atoms. Said polymethylene substituted by up to 4 of polymethylene or C ₁ -C ₄ alkyl, eg methyl;
E ₆ is an aliphatic or aromatic tetravalent group;
R _{2 in} formula (N) is already defined when m is 1;
G ₁ is a direct bond, C ₁ -C ₁₂ alkylene, phenylene or —NH—G′—NH, where G ′ is C ₁ -C ₁₂ alkylene.

Suitable tetraalkylpiperidine or tetraalkylpiperazine derivatives are, for example, compounds of the formulas 1-12:

の基を表すか、或いは
Ｒ₄がエチレンの場合、２つのＲ₅メチル置換基は、トリアジン架橋基−Ｎ（Ｒ₅）−Ｒ₄−Ｎ（Ｒ₅）−との直接結合により結合して、ピペラジン−１，４−ジイル基を形成することができ；
Ｒ₆は、Ｃ₂〜Ｃ₈アルキレンであるか又は下記の部分式：

の基を表すが、
但し、Ｒ₆が上記で示された構造である場合、Ｙは−ＯＨ以外であり；
Ａは、−Ｏ−又は−ＮＲ₇−であり、ここでＲ₇は、水素、直鎖若しくは分岐鎖Ｃ₁〜Ｃ₁₂アルキルであるか、又はＲ₇は、下記の部分式：

の基であり；
Ｔは、フェノキシ、１若しくは２つのＣ₁〜Ｃ₈アルキル若しくはＣ₁〜Ｃ₈アルコキシで置換されているフェノキシ又は−Ｎ（Ｒ₂）₂（ここでＲ₂は、水素以外であることが条件である）であるか又はＴは、下記の部分式：

の基であり；
Ｘは、−ＮＨ₂、−ＮＣＯ、−ＯＨ、−Ｏ−グリシジル又は−ＮＨＮＨ₂であり、そして
Ｙは、−ＯＨ、−ＮＨ₂、−ＮＨＲ₂（ここでＲ₂は水素以外である）であるか又はＹは−ＮＣＯ、−ＣＯＯＨ、オキシラニル、−Ｏ−グリシジル若しくは−Ｓｉ（ＯＲ₂）₃であるか；或いは
組み合わせＲ₃−Ｙ−は、−ＣＨ₂ＣＨ（ＯＨ）Ｒ₂（ここでＲ₂は、アルキル若しく１〜４個の酸素原子で中断されている前記アルキルである）であるか又はＲ₃−Ｙ−は、−ＣＨ₂ＯＲ₂であるか；或いは
ここでヒンダードアミン化合物は、Ｎ，Ｎ′，Ｎ′′′−トリス｛２，４−ビス〔（１−ヒドロカルビルオキシ−２，２，６，６−テトラメチルピペリジン−４−イル）アルキルアミノ〕−ｓ−トリアジン−６−イル｝−３，３′−エチレンジイミノジプロピルアミン；Ｎ，Ｎ′，Ｎ″−トリス｛２，４−ビス〔（１−ヒドロカルビルオキシ−２，２，６，６−テトラメチルピペリジン−４−イル）アルキルアミノ〕−ｓ−トリアジン−６−イル｝−３，３′−エチレンジイミノジプロピルアミンと下記式に記載される架橋誘導体の混合物であり、

Where
E ₁ , E ₂ , E ₃ and E ₄ are independently C ₁ -C ₄ alkyl or E ₁ and E ₂ are independently C ₁ -C ₄ alkyl, E ₃ and E ₄ Are pentamethylene together or E ₁ and E ₂ and E ₃ and E ₄ are together pentamethylene;
R ₁ is C _{1 to} C ₁₈ alkyl, C _{5 to} C ₁₂ cycloalkyl, a bicyclic or tricyclic hydrocarbon group having 7 to 12 carbon atoms, C _{7 to} C ₁₅ phenylalkyl, C _{6 to} C _10. Aryl or said aryl substituted with _{1 to} 3 C ₁ -C ₈ alkyl;
R ₂ is hydrogen or linear or branched C ₁ -C ₁₂ alkyl;
R ₃ is alkylene of 1 to 8 carbon atoms or R ₃ is —CO—, —CO—R ₄ —, —CONR ₂ — or —CO—NR ₂ —R ₄ —;
R ₄ is C ₁ -C ₈ alkylene;
R ₅ is hydrogen, linear or branched C ₁ -C ₁₂ alkyl, or the following partial formula:

Or when R ₄ is ethylene, the two R ₅ methyl substituents are bonded by a direct bond with the triazine bridging group —N (R ₅ ) —R ₄ —N (R ₅ ) —. A piperazine-1,4-diyl group can be formed;
R ₆ is C ₂ -C ₈ alkylene or the following partial formula:

Represents a group of
Provided that when R ₆ is the structure shown above, Y is other than —OH;
A is —O— or —NR ₇ —, wherein R ₇ is hydrogen, linear or branched C ₁ -C ₁₂ alkyl, or R ₇ is the following partial formula:

A group of
T is phenoxy, phenoxy substituted with 1 or 2 C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy, or —N (R ₂ ) ₂ (where R ₂ is other than hydrogen) Or T is the following sub-formula:

A group of
X is —NH ₂ , —NCO, —OH, —O-glycidyl or —NHNH ₂ , and Y is —OH, —NH ₂ , —NHR ₂ (where R ₂ is other than hydrogen). Or Y is —NCO, —COOH, oxiranyl, —O-glycidyl or —Si (OR ₂ ) ₃ ; or the combination R ₃ —Y— is —CH ₂ CH (OH) R ₂ (where R ₂ is alkyl or the alkyl interrupted by 1 to 4 oxygen atoms) or R ₃ —Y— is —CH ₂ OR ₂ ; or wherein the hindered amine compound is N, N ′, N ″ ′-tris {2,4-bis [(1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin-4-yl) alkylamino] -s-triazine-6 -Il} -3,3'-ethylenediiminodi N, N ', N "-tris {2,4-bis [(1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin-4-yl) alkylamino] -s-triazine-6 -Yl} -3,3'-ethylenediiminodipropylamine and a mixture of crosslinked derivatives described by the following formula:

であり；
Ｒは、メチル、プロピル、シクロヘキシル又はオクチル、例えばシクロヘキシルであり、
Ｒ₅は、Ｃ₁〜Ｃ₁₂アルキル、例えばｎ−ブチルであり；
ここで式（１４）及び（１５）の化合物において、Ｒがプロピル、シクロヘキシル又はオクチルである場合、
Ｔ及びＴ₁は、それぞれ、式１３において定義されたＲ₁〜Ｒ₄で置換されているテトラアミンであり、ここで、
（１）それぞれのテトラアミンにおけるｓ−トリアジン部分Ｅの１つは、２つのテトラアミンＴとＴ₁の間に架橋を形成する基Ｅ₁に代えられており；
Ｅ₁は、下記の部分式：

の基であるか、又は
（２）基Ｅ₁は、式１５と同じテトラアミンＴを両方の末端に有することができ、テトラアミンの２つのＥ部分は、１つのＥ₁基に代えられているか、又は
（３）テトラアミンＴの３つのｓ−トリアジン置換基は、全て、１つのＥ₁がＴ及びＴ₁に結合し、２番目のＥ₁がテトラアミンＴの両方の末端を有するようなＥ₁であることができ；
Ｌは、プロパンジイル、シクロヘキサンジイル又はオクタンジイルであり；
ここで化合物（１６）において、
Ｇ及びＧ₂が、Ｅ₁に代えられているｓ−トリアジン部分Ｅのうちの１つをそれぞれ有し、Ｇ₁が、Ｅ₁に代えられているトリアジン部分Ｅのうちの２つを有し、それによってＧとＧ₁の間に架橋があり、Ｇ₁とＧ₂の間に第２架橋があることを除いて、Ｇ、Ｇ₁及びＧ₂は、それぞれ、式Ｉにおいて定義されたＲ₁〜Ｒ₄で置換されたテトラアミンであり；
この混合物は、２〜４当量の２，４−ビス〔（１−ヒドロカルビルオキシ−２，２，６，６−テトラメチルピペリジン−４−イル）ブチルアミノ〕−６−クロロ−ｓ−トリアジンを、１当量のＮ，Ｎ′−ビス（３−アミノプロピル）エチレンジアミンと反応させることにより製造されるか；或いは
ヒンダードアミンは、式（１７）：

の化合物であり、
式中、指数ｎは、１〜１５の範囲であり；
Ｒ₁₂は、Ｃ₂〜Ｃ₁₂アルキレン、Ｃ₄〜Ｃ₁₂アルケニレン、Ｃ₅〜Ｃ₇シクロアルキレン、Ｃ₅〜Ｃ₇シクロアルキレン−ジ（Ｃ₁〜Ｃ₄アルキレン）、Ｃ₁〜Ｃ₄アルキレン−ジ（Ｃ₅〜Ｃ₇シクロアルキレン）、フェニレン−ジ（Ｃ₁〜Ｃ₄アルキレン）又は１，４−ピペラジンジイル、−Ｏ−若しくは＞Ｎ−Ｘ₁（ここでＸ₁は、Ｃ₁〜Ｃ₁₂アシル若しくは（Ｃ₁〜Ｃ₁₂アルコキシ）カルボニルであるか若しくは水素以外で下記のＲ₁₄に提示されている定義のうちの１つを有する）で中断されているＣ₄〜Ｃ₁₂アルキレンであるか、或いはＲ₁₂は、下記の部分式：

の基であり；
ここでＸ₂は、Ｃ₁〜Ｃ₁₈アルキル、非置換であるか又は１、２若しくは３つのＣ₁〜Ｃ₄アルキルで置換されているＣ₅〜Ｃ₁₂シクロアルキル、非置換であるか又は１、２若しくは３つのＣ₁〜Ｃ₄アルキル若しくはＣ₁〜Ｃ₄アルコキシで置換されているフェニル、非置換であるか又は１、２若しくは３つのＣ₁〜Ｃ₄アルキルでフェニルにおいて置換されているＣ₇〜Ｃ₉フェニルアルキルであり、そして
基Ｘ₃は、互いに独立して、Ｃ₂〜Ｃ₁₂アルキレンであり；
Ｒ₁₃、Ｒ₁₄及びＲ₁₅は、同一又は異なって、水素、Ｃ₁〜Ｃ₁₈アルキル、非置換であるか又は１、２若しくは３つのＣ₁〜Ｃ₄アルキルで置換されているＣ₅〜Ｃ₁₂シクロアルキル；Ｃ₃〜Ｃ₁₈アルケニル；非置換であるか又は１、２若しくは３つのＣ₁〜Ｃ₄アルキル若しくはＣ₁〜Ｃ₄アルコキシで置換されているフェニル；非置換であるか又は１、２若しくは３つのＣ₁〜Ｃ₄アルキルでフェニルにおいて置換されているＣ₇〜Ｃ₉フェニルアルキル；テトラヒドロフルフリル；又は−ＯＨ、Ｃ₁〜Ｃ₈アルコキシ、ジ（Ｃ₁〜Ｃ₄アルキル）アミノ若しくは下記の部分式：

の基により２、３若しくは４位で置換されているＣ₂〜Ｃ₄アルキルであり、
ここでＹは、−Ｏ−、−ＣＨ₂−、−ＣＨ₂ＣＨ₂−若しくは＞Ｎ−ＣＨ₃であるか又は−Ｎ（Ｒ₁₄）（Ｒ₁₅）は、追加的に下記：

の基であり；
基Ａは、互いに独立して、−ＯＲ₁₃、−Ｎ（Ｒ₁₄）（Ｒ₁₅）又は下記の部分式：

の基であり、
式中、
Ｘは、−Ｏ−または＞Ｎ−Ｒ₁₆であり、
Ｒ₁₆は、水素、Ｃ₁〜Ｃ₁₈アルキル、Ｃ₃〜Ｃ₁₈アルケニル、非置換であるか又は１、２若しくは３つのＣ₁〜Ｃ₄アルキルで置換されているＣ₅〜Ｃ₁₂シクロアルキル；非置換であるか又は１、２若しくは３つのＣ₁〜Ｃ₄アルキルでフェニルにおいて置換されているＣ₇〜Ｃ₉フェニルアルキル；テトラフルフリル；下記の部分式：

の基又は−ＯＨ、Ｃ₁〜Ｃ₈アルコキシ、ジ（Ｃ₁〜Ｃ₄アルキル）アミノ若しくは下記の部分式：

の基により２、３若しくは４位で置換されているＣ₂〜Ｃ₄アルキルであり；
Ｒ₁₁は、Ｒ₁₆で示された定義のうちの１つを有し；そして
基Ｂは、互いに独立して、Ａで示された定義のうちの１つを有する。 Here, in tetraamine (13),
R ₁ and R ₂ are s-triazine moieties E, one of R ₃ and R ₄ is s-triazine moiety E, and the other of R ₃ or R ₄ is hydrogen;
E is:

Is;
R is methyl, propyl, cyclohexyl or octyl, such as cyclohexyl,
R ₅ is C ₁ -C ₁₂ alkyl, such as n-butyl;
Here, in the compounds of the formulas (14) and (15), when R is propyl, cyclohexyl or octyl,
T and T ₁ are each a tetraamine substituted with R _{1 to} R ₄ as defined in Formula 13, where
(1) one of the s-triazine moieties E in each tetraamine is replaced by a group E ₁ that forms a bridge between the two tetraamines T and T ₁ ;
E ₁ is the following partial formula:

Or (2) the group E ₁ can have the same tetraamine T at both ends as in formula 15, and the two E moieties of the tetraamine are replaced by one E ₁ group, or (3) three s- triazine substituents of tetraamine T can all one E ₁ is bonded to T and T _1, 2 th E ₁ is at E ₁ so as to have the ends of both tetraamine T Can be;
L is propanediyl, cyclohexanediyl or octanediyl;
Here, in the compound (16),
G and G ₂ has a one of the s- triazine moiety E which is instead of the E ₁ each have G ₁ is two of the triazine moieties E that is instead of E ₁ whereby there is cross-linking between the G and G _1, except that there is a second bridge between in G ₁ and G _2, G, G ₁ and G ₂ are each as defined in formula I R A tetraamine substituted with _{1 to} R ₄ ;
This mixture contains 2-4 equivalents of 2,4-bis [(1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6-chloro-s-triazine, Prepared by reacting with 1 equivalent of N, N′-bis (3-aminopropyl) ethylenediamine; or the hindered amine is of formula (17):

A compound of
Where the index n is in the range of 1-15;
R ₁₂ is C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₅ -C ₇ cycloalkylene, C ₅ -C ₇ cycloalkylene-di (C ₁ -C ₄ alkylene), C ₁ -C ₄ alkylene. -Di (C ₅ -C ₇ cycloalkylene), phenylene-di (C ₁ -C ₄ alkylene) or 1,4-piperazinediyl, -O- or> N-X ₁ (where X ₁ is C _1- C ₄ -C ₁₂ alkylene interrupted by C ₁₂ acyl or (C ₁ -C ₁₂ alkoxy) carbonyl or having one of the definitions presented below for R ₁₄ other than hydrogen) Or R ₁₂ is the following sub-formula:

A group of
Wherein X ₂ is C ₁ -C ₁₈ alkyl, unsubstituted or C ₅ -C ₁₂ cycloalkyl, unsubstituted or substituted by _1, 2 or 3 C ₁ -C ₄ alkyl, or 1, 2, or phenyl substituted with three C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy, substituted in the phenyl by unsubstituted or 1, 2 or 3 C ₁ -C ₄ alkyl C ₇ -C ₉ phenylalkyl, and the groups X ₃ are, independently of one another, C ₂ -C ₁₂ alkylene;
R _13, R ₁₄ and R ₁₅ are the same or different, hydrogen, C ₁ -C ₁₈ alkyl, unsubstituted or is 1, 2 or 3 which is a C ₁ ~C ₄ C ₅ ~ substituted with alkyl C ₁₂ cycloalkyl; C ₃ -C ₁₈ alkenyl; phenyl that is unsubstituted or substituted with 1, 2 or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; unsubstituted or C ₇ -C ₉ phenylalkyl substituted on phenyl with _1, 2 or 3 C ₁ -C ₄ alkyl; tetrahydrofurfuryl; or —OH, C ₁ -C ₈ alkoxy, di (C ₁ -C ₄ alkyl) ) Amino or the following partial formula:

A C ₂ -C ₄ alkyl substituted in the 2, 3 or 4 position by a group of
Where Y is —O—, —CH ₂ —, —CH ₂ CH ₂ — or> N—CH ₃ , or —N (R ₁₄ ) (R ₁₅ ) is additionally:

A group of
The groups A are independently of each other —OR ₁₃ , —N (R ₁₄ ) (R ₁₅ ) or the following partial formula:

The basis of
Where
X is —O— or> N—R ₁₆ ;
R ₁₆ is hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₁₈ alkenyl, C ₅ -C ₁₂ cycloalkyl which is unsubstituted or substituted by _1, 2 or 3 C ₁ -C ₄ alkyl. A C ₇ -C ₉ phenylalkyl which is unsubstituted or substituted on the phenyl by _1, 2 or 3 C ₁ -C ₄ alkyl; tetrafurfuryl;

Or —OH, C ₁ -C ₈ alkoxy, di (C ₁ -C ₄ alkyl) amino or the following partial formula:

C ₂ -C ₄ alkyl substituted in the 2, 3 or 4 position by a group of
R ₁₁ has one of the definitions indicated by R ₁₆ ; and the group B, independently of one another, has one of the definitions indicated by A.

  Tetraalkylpiperidine and tetraalkylpiperazine compounds are known in the art and are described in US Pat. Nos. 5,004,770, 5,204,473, 5,096,950, No. 300,544, No. 5,112,890, No. 5,124,378, No. 5,145,893, No. 5,216,156, No. 5,844,026, Also known as N-alkoxy hindered amines and NOR hindered amines or NOR hindered amine light stabilizers or NOR-HALS, such as those disclosed in US 6,117,995 or US 6,271,377.

  U.S. Patent No. 6,271,377 and published U.S. Patent Application Nos. 09 / 505,529 (filed Feb. 17, 2000) and 09 / 794.710 (filed Feb. 27, 2001) ) Discloses hindered hydroxyalkoxyamine stabilizers. Hindered hydroxyalkoxyamine stabilizers are also known as N-hydroxyalkoxyhindered amines or NoRoI-HALS.

A typical structure is:

  Here, the definitions of R and R ′ include N-, O- or C-substituents.

When group E is —O—C (O) —C ₁ -C ₁₈ alkyl, the compound is a hydroxylamine ester.

  Hydroxylamine reacts with the acid derivative to form the final hydroxylamine ester. Such esterification methods are known and described in the literature.

  The preparation of certain suitable compounds is described in international patent application WO 01/90113.

の２，２，６，６−テトラアルキルピペリジン−１−オキシド、
下記式：

の１−ヒドロキシ−２，２，６，６−テトラアルキルピペリジン、
下記式：

の１−アルコキシ−２，２，６，６−テトラアルキルピペリジン、
下記式：

の１−アシルオキシ−２，２，６，６−テトラアルキルピペリジン
〔式中、
Ｒ_a及びＲ_bの一方は、
水素又はＮ置換基を表し、他方は、Ｏ置換基又はＣ置換基を表すか、或いは
Ｒ_a及びＲ_bは、両方とも、水素、Ｏ置換基又はＣ置換基を表し；
Ｒは、Ｃ₁〜Ｃ₂₀アルキル、Ｃ₅〜Ｃ₆シクロアルキル又は追加の置換基を有するＣ₂〜Ｃ₂₀アルキル、Ｃ₅〜Ｃ₆シクロアルキル若しくはＣ₂〜Ｃ₂₀アルケニルを表し；
Ａｃは、Ｃ₁〜Ｃ₂₀モノカルボン酸又はＣ₁〜Ｃ₂₀ジカルボン酸のアシル基を表し、Ｒ₁〜Ｒ₄は、それぞれＣ₁〜Ｃ₄アルキルを表し；
Ｒ₅及びＲ₆は、互いに独立して、水素又はＣ₁〜Ｃ₄アルキル、Ｃ₁〜Ｃ₃アルキルフェニル及びフェニルからなる群より選択される置換基を表し；そして
Ｒ₅及びＲ₆は、一緒になってオキソを表す〕
からなる群より選択される。 According to a preferred embodiment, the tetraalkylpiperidine derivative has the formula:

2,2,6,6-tetraalkylpiperidine-1-oxide of
Following formula:

Of 1-hydroxy-2,2,6,6-tetraalkylpiperidine,
Following formula:

1-alkoxy-2,2,6,6-tetraalkylpiperidine of
Following formula:

Of 1-acyloxy-2,2,6,6 -tetraalkylpiperidine [wherein
One of R _a and R _b is
Represents hydrogen or N substituent, the other represents O substituent or C substituent, or R _a and R _b both represent hydrogen, O substituent or C substituent;
R is, C ₁ -C ₂₀ represents alkyl, C ₂ -C ₂₀ alkyl having a C ₅ -C ₆ cycloalkyl or additional substituents, a C ₅ -C ₆ cycloalkyl or C ₂ -C ₂₀ alkenyl;
Ac represents an acyl group of C ₁ -C ₂₀ monocarboxylic acid or a C ₁ -C ₂₀ dicarboxylic acid, R ₁ to R ₄ each represent a C ₁ -C ₄ alkyl;
R ₅ and R ₆ independently of one another represent hydrogen or a substituent selected from the group consisting of C ₁ -C ₄ alkyl, C ₁ -C ₃ alkylphenyl and phenyl; and R ₅ and R ₆ are Together, represents oxo)
Selected from the group consisting of

According to a preferred embodiment, the composition comprises
One of R _a and R _b is
Represents hydrogen or N substituent, the other represents O substituent or C substituent, or R _a and R _b both represent hydrogen, O substituent or C substituent;
R is, C ₁ -C ₈ represents alkyl, C ₂ -C ₈ alkyl with C ₅ -C ₆ cycloalkyl or additional substituents, a C ₅ -C ₆ cycloalkyl or C ₂ -C ₈ alkenyl;
Ac is an acyl group of C ₁ -C ₈ carboxylic acid;
R _{1 to} R ₄ are each methyl; and R ₅ and R ₆ each contain at least one tetraalkylpiperidine derivative IIIa, IIIb, IIIc or IIId, each representing hydrogen, as component b).

According to a particularly preferred embodiment, the composition comprises
One of R _a and R _b is
Represents hydrogen or N substituent, the other represents O substituent or C substituent, or R _a and R _b both represent O substituent or C substituent;
R is, C ₁ -C ₈ represents alkyl, C ₅ -C ₆ cycloalkyl or C ₂ -C ₈ alkyl substituted with hydroxy, a C ₅ -C ₆ cycloalkyl or C ₂ -C ₈ alkenyl;
Ac is an acyl group of C ₁ -C ₈ carboxylic acid;
R _{1 to} R ₄ are each methyl; and R ₅ and R ₆ each contain at least one tetraalkylpiperidine derivative IIIa, IIIb, IIIc or IIId, each representing hydrogen, as component b).

の化合物、及び
下記式：

〔式中、ｎは１〜１５である〕の化合物
からなる群より選択される少なくとも１つのテトラアルキルピペリジン誘導体ＩＩＩｃ又はＩＩＩｄからなる。 According to a preferred embodiment, component b) is:
1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine,
Bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino) -s-triazine,
Bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate,
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6-chloro-s-triazine,
1- (2-hydroxy-2-methylpropoxy) -4-hydroxy-2,2,6,6-tetramethylpiperidine,
1- (2-hydroxy-2-methylpropoxy) -4-oxo-2,2,6,6-tetramethylpiperidine,
1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,
Bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) sebacate,
Bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) adipate,
2,4-bis {N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] -N-butylamino} -6- (2- Hydroxyethylamino) -s-triazine,
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6-chloro-s-triazine and N, N'-bis (3-amino Propyl) ethylenediamine) reaction product,
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino) -s-triazine,
2,4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine) and 2-chloro-4,6-bis (dibutylamino) -s-triazine end-capped An oligomeric compound which is a condensate with 4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -s-triazine;
Following formula:

And the following formula:

It consists of at least one tetraalkylpiperidine derivative IIIc or IIId selected from the group consisting of compounds wherein n is 1-15.

  The compounds described above are partly commercially available items. Exemplary compounds are marketed by Ciba under the trade name Flametab NOR 116 (R), Tinuvin NOR 371 (R) or lrgatec CR 76 (R).

  Component b) is preferably 0.01 to 10.0% by weight, more preferably 0.1 to 9.0% by weight, most preferably 0.25, based on the weight of polymer substrate component c). It is contained in the flame retardant composition of the present invention in an amount of ˜3.0 mass%.

Component c)
The term polymer substrate includes within its scope thermoplastic polymers or thermosetting resins. A list of suitable thermoplastic polymers is presented below:
1. Polymers of monoolefins and diolefins such as polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, and polymers of cycloolefins such as Polymers of cyclopentene or norbornene, polyethylene (optionally cross-linked), eg high density polymethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultra high molecular weight polyethylene (HDPE-UHMW), medium Density polyethylone (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).

  The polyolefins exemplified in the previous paragraph, ie polymers of monoolefins, preferably polyethylene and polypropylene, can be prepared by different methods, in particular by the following methods.

  a) radical polymerization (usually under high pressure and high temperature).

  b) Catalytic polymerization using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals are usually one or more ligands, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, which may be either π- or σ-coordinated. , Alkenyl and / or aryl. These metal complexes may be in free form or immobilized on a substrate, typically activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide. These catalysts can be soluble or insoluble in the polymerization medium. The catalyst can itself be used for polymerization or can use further activators, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyl oxanes, The metal is an element of group Ia, IIa and / or IIIa of the periodic table. The activator can be conveniently modified with further ester, ether, amine or silyl ether groups. These catalyst systems are commonly referred to as Phillips, Standard Oil Indiana, Ziegler-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

  2. Mixtures of the polymers described in 1), for example mixtures of polypropylene and polyisobutylene, mixtures of polypropylene and polyethylene (for example PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (for example LDPE / HDPE).

  3. Mutual copolymers of monoolefins and diolefins or copolymers of other vinyl monomers, such as ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene / But-1-ene copolymer, propylene / isobutylene copolymer, ethylene / but-1-ene copolymer, ethylene / hexene copolymer, ethylene / methylpentene copolymer, ethylene / heptene copolymer, ethylene / octene copolymer, ethylene / vinylcyclohexane copolymer, ethylene / Cycloolefin copolymer (eg, ethylene / norbornene such as COC), ethylene / 1-olefin copolymer (where 1-olefin is generated in situ), Pyrene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / vinylcyclohexene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers or ethylene / acrylic acid copolymers and their salts (ionomers); Terpolymers of ethylene and propylene and dienes such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with each other and with the polymers described in 1) above, such as polypropylene / ethylene- Propylene copolymer, LDPE / ethylene-vinyl acetate copolymer (EVA), LDPE / ethylene-acrylic acid copolymer (EAA), LLDPE / E A, LLDPE / EAA, and alternating or random polyalkylene / carbon monoxide copolymers and mixtures thereof with other polymers, for example mixtures of polyamide.

4). Hydrocarbon resins (eg C ₅ -C ₉ ) and their mixtures of polyalkylenes and starch containing their hydrogenated reformate (eg tackifier).

  The homopolymers and copolymers described above can have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic, with atactic polymers being preferred. Stereo block polymers are also included.

  5. Polystyrene, poly (p-methylstyrene), poly (α-methylstyrene).

  6). Vinyl aromatic monomers including all isomers of styrene, α-methylstyrene, vinyltoluene, especially p-vinyltoluene, all isomers of ethylstyrene, propylstyrene, vinylbiphenyl, vinylnaphthalene and vinylanthracene and mixtures thereof Aromatic homopolymers and copolymers derived from Homopolymers and copolymers can have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic, with atactic polymers being preferred. Stereo block polymers are also included.

  a) Copolymers comprising the aforementioned vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydride, maleimides, vinyl acetate and vinyl chloride or acrylic acid derivatives, and mixtures thereof, such as , Styrene / butadiene, styrene / acrylonitrile, styrene / ethylene (copolymer), styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / Methyl acrylate; impact styrene copolymer and other polymer mixtures such as polyacrylates, diene polymers or ethylene / propylene / diene terpolymers; and block copolymers of styrene, Example, styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.

  b) Hydrogen derived from hydrogenation of the polymer described in 6), in particular including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH). Aromatic polymers.

  c) Hydrogenated aromatic polymers derived by hydrogenation of the polymers described in 6a). Homopolymers and copolymers can have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic, with atactic polymers being preferred. Stereo block polymers are also included.

  7). Graft copolymers of vinyl aromatic monomers such as styrene or α-methylstyrene, eg, styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymer; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; Styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylate or methacryl on polybutadiene Acid alkyl; styrene and acrylonitrile on ethylene / propylene / diene terpolymers; Styrene and acrylonitrile on alkyl oxalates or polyalkyl methacrylates; styrene and acrylonitrile on acrylate / butadiene copolymers and their mixtures with the copolymers shown in 6), for example as ABS, MBS, ASA or AES polymers Known copolymer mixture.

  8). Halogen containing polymers such as polychloroprene, chlorinated rubber, chlorinated and brominated copolymers of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- And copolymers, in particular polymers of halogen-containing vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, and copolymers thereof, such as vinyl chloride / vinylidene chloride, vinyl / vinyl acetate or vinylidene chloride / Vinyl acetate copolymer.

  9. Polymers derived from α, β-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates; polymethyl methacrylate, polyacrylamide and polyacrylonitrile with improved impact resistance by butyl acrylate.

  10. Copolymers of the monomers described in 9) with one another or with other unsaturated monomers, such as acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide copolymers Or acrylonitrile / alkyl methacrylate / butadiene terpolymer.

  11. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, vinyl polymaleate, polyvinyl butyral, polyallyl phthalate or polyallyl Melamine; and their copolymers with the olefins described in 1 above.

  12 Homopolymers and copolymers of cyclic ethers such as copolymers with polyalkylene glycols, polyethylene oxide, polypropylene oxide or bisglycidyl ethers.

  13. Polyacetals such as polyoxymethylene and polyoxymethylene containing ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

  14 Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxide and styrene polymers or polyamides.

  15. Polyurethanes, one derived from hydroxyl-terminated polyethers, polyesters or polybutadiene and the other derived from aliphatic or aromatic polyisocyanates, and their precursors.

  16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamide starting from m-xylenediamine and adipic acid; hexamethylenediamine and isophthalic acid and / or with or without elastomer as modifier Polyamides made from terephthalic acid, such as poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; also the aforementioned polyamides and polyolefins, olefin copolymers, ionomers or chemistry Combined Or block copolymers with grafted elastomers; or polyethers, such as block copolymers with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; and polyamides or copolyamides modified with EPDM or ABS And polyamides that are condensed during processing (RIM polyamide system).

  17. Polyurea, polyimide, polyamideimide, polyetherimide, polyesterimide, polyhydantoin and polybenzimidazole.

  18. Polyesters derived from dicarboxylic acids and diols and / or derived from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylol cyclohexane terephthalate, polyalkylene naphthalate (PAN) ) And polyhydroxybenzoates, and block copolyetheresters derived from hydroxyl-terminated polyethers; also polyesters modified with polycarbonate or MBS.

  19. Polyketones.

  20. Polysulfone, polyethersulfone and polyetherketone.

  21. Blends (polyblends) of the aforementioned polymers, such as PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT , PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC.

に対応するポリカーボネート類。 22. The following general formula:

Polycarbonates corresponding to

  Such polycarbonates are obtained by interfacial processes or melt processes (catalytic transesterification). The polycarbonate can be branched or linear in structure and can contain any functional substituent. Polycarbonate copolymers and polycarbonate blends are also within the scope of the present invention. The term polycarbonate should be construed to include copolymers and blends with other thermoplastic resins. Polycarbonate can be produced by, for example, US Pat. Nos. 3,030,331, 3,169,121, 4,130,458, 4,263,201, and 4,286. No. 083, No. 4,552,704, No. 5,210,268 and No. 5,606,007. A combination of two or more different molecular weight polycarbonates can be used.

  Preference is given to the reaction of diphenols such as bisphenol A with a carbonate source. Examples of suitable diphenols are:

  The carbonate source can be a carbonyl halide, a carbonate ester or a haloformate. Suitable carbonate halides are phosgene or carbonyl bromide. Suitable carbonates are: dialkyl carbonates such as dimethyl- or diethyl carbonate, diphenyl carbonates, phenyl-alkylphenyl carbonates such as phenyl-tolyl carbonate, dialkyl carbonates such as dimethyl- or diethyl carbonate, di- (chlorophenyl) carbonates Di- (halophenyl) carbonates such as di- (bromophenyl) carbonate, di- (trichlorophenyl) carbonate or di- (trichlorophenyl) carbonate, di-tolyl carbonate, naphthyl carbonate, dichloronaphthyl carbonate (Alkylphenyl) carbonate and the like.

  The polymer substrate described above comprising a polycarbonate or polycarbonate blend is a polycarbonate copolymer and there is an isophthalate / terephthalate-resorcinol segment. Such polycarbonates are commercially available, for example Lexan® SLX (General Electrics Co. USA). Other polymer substrates of component b) include a wide variety including polyolefins, polystyrenes, polyesters, polyethers, polyamides, poly (meth) acrylates, thermoplastic polyurethanes, polysulfones, polyacetals and PVC (with appropriate compatibilizers). Such synthetic polymers can additionally be included in the form of mixtures or copolymers. For example, the polymer substrate can additionally contain a thermoplastic polymer selected from the group of resins consisting of polyolefins, thermoplastic polyurethanes, styrene polymers and copolymers thereof. Specific embodiments include polypropylene (PP), polyethylene (PE), polyamide (PA), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), glycol modified polycyclohexylene methylene terephthalate (PCTG), polysulfone (PSU). ), Polymethyl methacrylate (PMMA), thermoplastic polyurethane (TPU), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-styrene-acrylic acid ester (ASA), acrylonitrile-ethylene-propylene-styrene (AES), styrene-anhydrous Maleic acid (SMA) or high impact polystyrene (HIPS) is included.

の少なくとも２つのエポキシ基が存在し、これは炭素、酸素、窒素又は硫黄原子に直接結合しており、ここで、ｑは、０を表し、Ｒ₁及びＲ₃は、両方とも水素を表し、そしてＲ₂は、水素若しくはメチルを表すか又はｑは、０若しくは１を表し、Ｒ₁及びＲ₃は、一緒になって、−ＣＨ₂−ＣＨ₂−若しくは−ＣＨ₂−ＣＨ₂−ＣＨ₂−の基を形成し、そしてＲ₂は、水素を表す。 23. It is an epoxy resin composed of a bifunctional or polyfunctional epoxy compound, and the following partial formula:

There are at least two epoxy groups of which are directly bonded to a carbon, oxygen, nitrogen or sulfur atom, where q represents 0, R ₁ and R ₃ both represent hydrogen, R ₂ represents hydrogen or methyl, or q represents 0 or 1, and R ₁ and R ₃ together represent —CH ₂ —CH ₂ — or —CH ₂ —CH ₂ —CH _2. -And R ₂ represents hydrogen.

  Suitable hardener components include, for example, amines and anhydride hardeners such as polyamines such as ethylenediamine, diethylenetriamine, triethylenetriamine, hexamethylenediamine, methanediamine, N-aminoethylpiperazine, diaminodiphenylmethane [DDM], Alkyl-substituted derivatives of DDM, isophoronediamine [IPD], diaminodiphenylsulfone [DDS], 4,4'-methylenedianiline [MDA] or m-phenylenediamine [MPDA], polyamide, alkyl / alkenylimidazole, dicyandiamide [DICY] 1,6-hexamethylene-bis-cyanoguanidine or acid anhydrides such as dodecenyl succinic acid anhydride, hexahydrophthalic acid anhydride, tetrahydrophthalic acid anhydride, phthalic acid anhydride, pyro Litho anhydride and derivatives thereof.

  A preferred embodiment of the invention relates to a composition comprising a thermoplastic polymer as component c). Preferred thermoplastic polymers include polyolefin homo- and copolymers, copolymers of olefin vinyl monomers, styrene homopolymers and copolymers thereof.

  Advantageously, the melamine and guanidine salts (I) and (II) are ground to a fine powder with an average particle size of less than 100 μm prior to application to the polymer substrate, which makes the flame retardant properties of the composition of the invention This is because it is observed that the particle size is improved by a small particle size.

Additional components The present invention is selected from the group consisting of optional flame retardants, so-called anti-dripping agents and polymer stabilizers in addition to components a), b) and c) as defined above. It further relates to a composition comprising further additives.

Typical phosphorus-containing flame retardants are, for example:
Tetraphenyl resorcinol diphosphate (Fyrolflex® RDP, Akzo Nobel), resorcinol diphosphate oligomer (RDP), triphenyl phosphate, tris (2,4-di-tert-butylphenyl) phosphate, ethylenediamine diphosphate (EDAP) , ammonium polyphosphate, diethyl -N, N-bis (2-hydroxyethyl) - amino - methyl phosphonate, hydroxyalkyl esters of phosphoric acid, di -C ₁ -C ₄ alkyl phosphinic acid and hypophosphoric acid (H ₃ PO ₂ ) salts, in particular Ca ²⁺ , Zn ²⁺ or Al ³⁺ salts, tetrakis (hydroxymethyl) phosphonium sulfide, triphenylphosphine, 9,10-dihydro-9-oxa-10-phosphorylphenanthrene. Derivatives of -10-oxide (DOPO) and phosphazene flame retardants.

  The nitrogen-containing flame retardant is, for example, an isocyanurate flame retardant such as polyisocyanurate, an ester of isocyanuric acid or isocyanurate. Representative examples are hydroxyalkyl isocyanurates such as tris- (2-hydroxyethyl) isocyanurate, tris (hydroxymethyl) isocyanurate, tris (3-hydroxy-n-propyl) isocyanurate or triglycidyl isocyanurate. is there.

  Nitrogen-containing flame retardants further include flame retardants based on melamine. Representative examples are melamine cyanurate, melamine borate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine ammonium polyphosphate, melamine ammonium pyrophosphate, dimelamine phosphate and dimelamine pyrophosphate.

  Further examples are benzoguanamine, tris (hydroxyethyl) isocyanurate, allantoin, glycoluril, melamine cyanurate, melamine phosphate, dimelamine phosphate, urea cyanurate, ammonium polyphosphate, melem, melam, melon series condensates and And / or a highly condensed product or reaction product of melamine and phosphoric acid, or a mixture thereof.

Typical organohalogen flame retardants are, for example:
Polybrominated diphenyl oxide (DE-60F, Great Lakes Corp.), decabromodiphenyl oxide (DBDPO; Saytex® 102E), tris [3-bromo-2,2-bis (bromomethyl) propyl] phosphate (PB) 370 (registered trademark), FMC Corp.), tris (2,3-dibromopropyl) phosphate, tris (2,3-dichloropropyl) phosphate, chlorendic acid, tetrachlorophthalic acid, tetrabromophthalic acid, poly-β- Chloroethyl triphosphonate mixture, tetrabromobisphenol A bis (2,3-dibromopropyl ether) (PE68), brominated epoxy resin, ethylene-bis (tetrabromophthalimide) (Saytex® BT-93), bis (F Sachlorocyclopentadieno) cyclooctane (Dechlorene Plus (registered trademark)), chlorinated paraffin, octabromodiphenyl ether, hexachlorocyclopentadiene derivative, 1,2-bis (tribromophenoxy) ethane (FF680), tetrabromo-bisphenol A (Saytex® RB100), ethylene bis- (dibromo-norbornane dicarboximide) (Saytex® BN-451), bis- (hexachlorocycloentadeno) cyclooctane, PTFE, tris- (2, 3-Dibromopropyl) -isocyanurate and ethylene-bis-tetrabromophthalimide.

The organohalogen flame retardants described above are routinely combined with inorganic oxide synergists. Most customary for this use are zinc oxide or antimony oxide, such as Sb ₂ O ₃ or Sb ₂ O ₅ . Boron compounds are also suitable.

Typical inorganic flame retardants include, for example, aluminum trihydroxide (ATH), boehmite (AlOOH), magnesium dihydroxide (MDH), zinc borate, CaCO ₃ , (organically modified) layered silicic acid Salts, layered double hydroxides (organically modified) and mixtures thereof are included.

  The class of additional flame retardants described above is from about 0.5% to about 60.0% of the weight of the organic polymer substrate, such as from about 1.0% to about 40.0%, such as polymer weight or It is advantageously included in the compositions of the present invention in an amount of about 5.0% to about 35.0% based on the total weight of the composition.

  According to another embodiment, the invention relates to a composition additionally comprising a so-called anti-drip agent as an additional component.

  These anti-drip agents reduce the melt flow of the thermoplastic polymer and suppress the formation of droplets at high temperatures. Various references such as US Pat. No. 4,263,201 describe the addition of anti-dripping agents to flame retardant compositions.

  Suitable additives that inhibit the formation of droplets at high temperatures include glass fibers, polytetrafluoroethylene (PTFE), high temperature elastomers, carbon fibers, glass spheres, and the like.

  The addition of polysiloxanes of different structures has been proposed in various references (see US Pat. Nos. 6,660,787, 6,727,302 or 6,730,720). ).

  Stabilizers are preferably halogen free and are nitroxyl stabilizers, nitrone stabilizers, amine oxide stabilizers, benzofuranone stabilizers, phosphite and phosphonite stabilizers, quinone methide stabilizers, and 2,2'-alkylidene bisphenol stabilizers. Selected from the group consisting of monoacrylate esters of the agent.

  As described above, the composition of the present invention can be, for example, a pigment, dye, plasticizer, antioxidant, thixotropic agent, leveling aid, basic co-stabilizer, metal passivator, metal oxide. Organophosphorus compounds, further light stabilizers and mixtures thereof, in particular pigments, phenolic antioxidants, calcium stearate, zinc stearate, 2-hydroxy-benzophenone, 2- (2'-hydroxyphenyl) benzotriazole and One or more conventional additives selected from UV absorbers based on 2- (2-hydroxyphenyl) -1,3,5-triazine groups may additionally be included.

  Preferred additional additives for the compositions defined above are processing stabilizers such as the phosphites and phenolic antioxidants described above, and light stabilizers such as benzotriazole. Preferred specific antioxidants include octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANOX 1076), pentaerythritol tetrakis [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate] (IRGANOX 1010), tris (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate (IRGANOX 3114), 1,3,5-trimethyl-2,4 6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (IRGANOX 1330), triethylene glycol-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ] (IRGANOX 245) and N, N'-hexane-1,6-diyl-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide] (IRGANOX 1098) is included. Specific processing stabilizers include tris (2,4-di-tert-butylphenyl) phosphite (IRGAFOS 168), 3,9-bis (2,4-di-tert-butylphenoxy) -2,4, 8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane (IRGAFOS 126), 2,2 ', 2 "-nitrilo [triethyl-tris (3,3', 5,5'-tetra-tert- Butyl-1,1'-biphenyl-2,2'-diyl)] phosphite (IRGAFOS 12) and tetrakis (2,4-di-tert-butylphenyl) [1,1-bisphenyl] -4,4 ' -Diylbisphosphonite (IRGAFOS P-EPQ), specific light stabilizers include 2- (2H-benzotriazol-2-yl) -4,6-bis 1-methyl-1-phenylethyl) phenol (TINUVIN 234), 2- (5-chloro- (2H) -benzotriazol-2-yl) -4- (methyl) -6- (tert-butyl) phenol (TINUVIN) 326), 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (TINUVIN 329), 2- (2H-benzotriazol-2-yl)- 4- (tert-butyl) -6- (sec-butyl) phenol (TINUVIN 350), 2,2'-methylenebis (6- (2H-benzotriazol-2-yl) -4- (1,1,3 3-tetramethylbutyl) phenol) (TINUVIN 360), 2- (4,6-diphenyl-1,3,5-triazine-2-y ) -5-[(hexyl) -oxy] -phenol (TINUVIN 1577), 2- (2'-hydroxy-5'-methylphenyl) benzotriazole (TINUVIN P), 2-hydroxy-4- (octyloxy) benzophenone (CHIMASSORB 81), 1,3-bis-[(2'-cyano-3 ', 3'-diphenyl-acryloyl) oxy] -2,2-bis-{[(2'-cyano-3', 3 ' -Diphenylacryloyl) oxy] methyl} -propane (UVINUL 3030, BASF), ethyl-2-cyano-3,3-diphenyl acrylate (UVINUL 3035, BASF) and (2-ethylhexyl) -2-cyano-3,3- Diphenyl acrylate (UVINUL 3039, BASF) is included.

  The additives described above are preferably contained in an amount of 0.001 to 10.0%, in particular 0.05 to 5.0%, relative to the mass of the polymer substrate of component c).

  Incorporation of the above-defined components into the polymer component may be dry mixing in the form of a powder or wet mixing, for example in the form of a solution, dispersion or suspension in an inert solvent, water or oil. It is carried out by a known method. Additive components a) and b), and any further additives can be incorporated, for example before or after molding, or a dissolved or dispersed additive or additive mixture is applied to the polymer material, followed by a solvent or It is also possible to incorporate the suspending / dispersing agent with or without evaporation. They can be added directly to the processing equipment (eg extruders, closed mixers, etc.), for example as a dry mixture or powder, or as a solution or dispersion or suspension or melt.

  Addition of the additive components to the polymer substrate can be carried out with a conventional mixer where the polymer is melted and mixed with the additive. Suitable machines are known to those skilled in the art. These are mainly mixers, kneaders and extruders.

  Processing is preferably carried out by an extruder with the introduction of additives during processing.

  Particularly preferred processing machines are a single screw extruder, a reversing and co-rotating twin screw extruder, a planetary gear extruder, an annular extruder or a co-kneader. A processing machine with at least one gas removal section can be used, to which a vacuum can be applied.

  Suitable extruders and kneaders are described, for example, in Handbuch der Kunststoffextension, Vol. Hensen, W.H. Knappe, H.C. Potente, 1989, pp. 3-7, ISBN: 3-446-14339-4 (Volume 2: Extrassagen 1986, ISBN 3-446-14329-7).

  For example, the screw length is 1-60 screw diameters, preferably 35-48 screw diameters. The rotational speed of the screw is preferably 10 to 600 revolutions per minute (rpm), preferably 25 to 300 rpm.

  Maximum throughput depends on screw diameter, rotational speed and driving force. The method of the present invention can also be carried out at a level below the maximum throughput using a meter that changes the described parameters or delivers a dose.

  If multiple ingredients are added, they can be premixed or added individually.

  The additive component a) and any further additives can also be sprayed onto the polymer substrate b). The additive mixture can dilute other additives such as the conventional additives shown above or melts thereof, and can also be sprayed onto the polymer substrate together with those additives. . It is particularly advantageous to add by spraying during the deactivation of the polymerization catalyst, in which case the released steam may be used for deactivation of the catalyst. In the case of spherically polymerized polyolefins, for example, it may be advantageous to apply the additives according to the invention by spraying, optionally together with other additives.

  Additive components a) and b) and any further additives are incorporated into the polymer at a concentration of about 1.0% to about 40.0%, preferably 2.0% to about 20.0% by weight. It can also be added to the polymer in the form of a masterbatch ("concentrate") that contains the components. The polymer need not have the same structure as the polymer to which the additive is ultimately added. In such operations, the polymer can be used in the form of powders, granules, solutions and suspensions or in the form of latex.

  The incorporation can take place before or during the shaping operation. The material containing the additive of the present invention described herein is preferably a molded article, such as a rotational molded article, an injection molded article, a cross-sectional agent, etc., in particular of fibers, molten nonwovens, films or foams. Used for manufacturing.

の化合物、及び
下記式：

〔式中、ｎは１〜１５である〕の化合物
からなる群より選択される少なくとも１つのテトラアルキルピペリジン誘導体ＩＩＩｃ又はＩＩＩｄと；
ｃ）多官能エポキシド化合物、ヒンダード化合物及び熱可塑性ポリマーからなる群より選択されるポリマー基材と
を含む組成物に関する。 Particularly preferred embodiments of the present invention are:
a) phenylphosphonate (I ′) or (II ′);
b) The following:
1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine,
Bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino) -s-triazine,
Bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate,
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6-chloro-s-triazine,
1- (2-hydroxy-2-methylpropoxy) -4-hydroxy-2,2,6,6-tetramethylpiperidine,
1- (2-hydroxy-2-methylpropoxy) -4-oxo-2,2,6,6-tetramethylpiperidine,
1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,
Bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) sebacate,
Bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) adipate,
2,4-bis {N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] -N-butylamino} -6- (2- Hydroxyethylamino) -s-triazine,
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6-chloro-s-triazine and N, N'-bis (3-amino Propyl) ethylenediamine) reaction product,
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino) -s-triazine,
2,4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine) and 2-chloro-4,6-bis (dibutylamino) -s-triazine end-capped An oligomeric compound which is a condensate with 4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -s-triazine;
Following formula:

And the following formula:

At least one tetraalkylpiperidine derivative IIIc or IIId selected from the group consisting of compounds wherein n is 1 to 15;
c) A composition comprising a polyfunctional epoxide compound, a hindered compound and a polymer substrate selected from the group consisting of thermoplastic polymers.

Further embodiments of the present invention are:
a) The following:
a ') melamine phenylphosphonate (I) and b') guanidine phenylphosphonate (II)
〔here,
R _{1 to} R ₅ independently of one another represent hydrogen or a substituent selected from the group consisting of C ₁ -C ₄ alkyl, hydroxy, hydroxy-C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy;
R _{6 to} R ₉ are independently of each other hydrogen or C ₁ -C ₄ alkyl, phenyl, phenyl-C ₁ -C ₄ alkyl, (C ₁ -C ₄ alkyl) _1-3 phenyl and (C ₁ -C ₄ alkyl) represents a substituent selected from the group consisting of _1-2 hydroxyphenyl; and x represents a number from 1.0 to 2.0.
A phenylphosphonate selected from the group consisting of:
b) 2,2,6,6-tetraalkylpiperidine-1-oxide, 1-hydroxy-2,2,6,6-tetraalkylpiperidine, 1-alkoxy-2,2,6,6-tetraalkylpiperidine and A tetraalkylpiperidine derivative selected from the group consisting of 1-acyloxy-2,2,6,6- tetraalkylpiperidine ;
Relates to a mixture comprising

  Components a) and b) are from 0.1 to 45.0% by weight in component a), preferably from 0.1 to 30.0% by weight, in component b) from 0.05 to 5.0% by weight, Preferably it is mixed with the polymer substrate c) at a concentration of 0.1 to 2.0% by weight.

  Preferred ratios of components a): b) are in the range of 50: 1 to 1: 5, preferably 20: 1 to 1: 2.

  A further embodiment of the invention is a method for imparting flame retardancy to a polymer substrate, comprising adding a mixture of components a) and b) as defined above to a polymer substrate of component c). Relates to the method of inclusion.

  The following examples illustrate the invention but should not be construed as limiting its scope.

Examples Components and Reagents Used Moplen® HF500 N: Commercial Polypropylene (Basell, Germany)
BB 412E: Commercially available polypropylene block copolymer (Borealis AG, Austria)
Melamine: a commercial product (DSM, Netherlands)
Guanidine carbonate: a commercial product (Merck Eurolab, Germany)
Phenylphosphonic acid: a commercial product (Aldrich, Germany)
Tinuvin® NOR 371 (NOR 1): a commercial product (Ciba Inc., Switzerland)
Flamestab® NOR 116 (NOR 2): a commercial product (Ciba Inc., Switzerland)
2,4,6-tris (1-methoxy-2,2,6,6-tetramethylpiperidin-4-yloxy) -1,3,5-triazine (NOR) obtained according to US Pat. No. 5,019,613 3)
Bis (1-propoxy-2,2,6,6-tetramethylpiperidyl) -4-diazene (NOR 4) obtained according to WO2008 / 101845

Preparation of Phenylphosphonate Example A: Preparation of Melamine Phenylphosphonate Melamine (2.0 mol, 252.0 g) is dispersed in 2.50 l of deionized water and heated to 95 ° C. To this dispersion, phenylphosphonic acid (2.00 mol, 316.0 g) is added in small portions with vigorous stirring. After the addition is complete, the reaction mixture is stirred at 95 ° C. for an additional 90 minutes and then cooled to 60 ° C. The formed crystals are filtered off at 60 ° C. and dried at 130 ° C. under vacuum. 514.0 g (1.81 mol, 90.4%) of product are obtained as a colorless solid with a decomposition temperature of 281 ° C. (onset).
Elemental analysis of C ₉ H ₁₃ N ₆ O ₃ P (284.22) P (calculated value): 10.9%; P (actual value): 10.7%.

Example B: Preparation of guanidine phenylphosphonate Guanidine carbonate (1.25 mol, 225.0 g) is dispersed in 250 ml of deionized water and heated to 50 ° C. A saturated solution of phenylphosphonic acid (2.50 mol, 395 g) in water at 50 ° C. is prepared and added to this dispersion in small portions with vigorous stirring. After the addition is complete, the reaction mixture is stirred for an additional 90 minutes at 50 ° C. and then cooled to room temperature. The solution is poured into 3 l of acetone, the precipitate is filtered off and dried at 130 ° C. under vacuum. 520.0 g (2.39 mol, 95.7%) of product are obtained as a colorless solid having a melting point of 140 ° C. and a decomposition temperature of 275 ° C. (onset).

Example C: Preparation of diguanidine phenylphosphonate Guanidine carbonate (1.39 mol, 250.0 g) is dispersed in 250 ml of deionized water and heated to 95 ° C. A 70 ° C. solution of phenylphosphonic acid (1.39 mol, 220.0 g) in 100 ml of water is prepared and added in small portions with vigorous stirring. After the addition is complete, the reaction mixture is stirred at 95 ° C. for an additional 30 minutes and cooled to room temperature. The formed crystals are filtered off and dried at 130 ° C. under vacuum. 350.0 g (1.27 mol, 91.2%) of the product is obtained as a colorless solid with a decomposition temperature of 259 ° C. (onset).

Test Method for Evaluating Flame Retardancy UL94 test according to “Flammability of Plastic Materials for Parts in Devices and Applications”, 5th edition, October 29, 1996. The ranking according to the UL94V test is summarized in the following table (time is shown for one specimen).

ｎ．ｃ．：分類なし

n. c. : No classification

Preparation of Polymer Composition The melamine and guanidine salts prepared according to Examples AC are ground and sieved using a 120 μm sieve. Prior to use, the resulting powder is dried in a vacuum oven at 80 ° C. overnight.

Extrusion Reference Examples 1 to 5 and Examples 1 to 7 of the present invention: Polypropylene homopolymer (MOPLEN HF 500 N) was fed by a co-rotating twin screw extruder ZSK25 (Coperion Werner & Pfleiderer) at a temperature T _{max of} 230 ° C, Extrude at a throughput of h and a rotational speed of 100 revolutions per minute (rpm). MOPLEN HF 500 N contains basic level stabilizers (0.05% calcium stearate + 0.5% IRGANOX® B225; IRGANOX® B225 is a combination of IRGAFOS® 168 and IRGANOX® Add 1010) 1: 1 mixture) and the additives listed in Table 2 .

Reference Examples 6 to 12 and Examples 8 to 12 of the present invention: Polypropylene homopolymer (MOPLEN HF 500 N) was fed into a co-rotating twin screw extruder ZSK18 (Coperion Werner & Pfleiderer) at a temperature T _{max of} 230 ° C., 2 kg / h And at a rotational speed of 100 revolutions per minute (rpm). MOPLEN HF 500 N contains basic level stabilizers (0.05% calcium stearate + 0.3% IRGANOX® B225; IRGANOX® B225 is a combination of IRGAFOS® 168 and IRGANOX® Add the additives shown in Table 4 and Table 5 ).

Reference Examples 13-15 and Examples 13-14 of the present invention: Polypropylene block copolymer (BB 412 E) with no additional stabilizer and with the additives shown in Table 6 , co-rotating biaxial Extrusion is performed by a screw extruder ZSK25 (Coperion Werner & Pfleiderer) at a temperature T _{max of} 250 ° C., a throughput of 4 kg / h and a rotation speed of 100 revolutions per minute (rpm).

  After cooling in a water bath, the polymer strand is granulated. UL94-V specimens (bar 125 x 12.5 mm, thickness = 1.6 mm) and 1.0 mm platelets according to DIN 4102-B2 are prepared by injection molding at 230 ° C on an Arburg 370S injection molding machine. A film according to DIN 4102-B2 is obtained by compression molding.

Testing polymer compositions Test samples are conditioned for 48 hours at 23 ° C. and 50% relative humidity and then examined for flame retardant behavior according to UL94-V standards.

An additional UL94-V test is performed after exposing the specimens to deionized water at 70 ° C. for 7 days (leach test). Subsequently, the test bar is dried in a vacuum oven at 105 ° C. for 24 hours. The results obtained after leaching are shown in Table 3 .

Table 2
UL94V (1.6 mm) test results obtained with polypropylene homopolymers containing different flame retardant compositions

  It can be concluded from the results reported above that the polymer composition of the present invention exhibits excellent flame retardancy with self-extinguishing properties. None of the reference compositions containing a single additive showed significant flame retardant behavior, but the inventive combination of phosphonates and representative sterically hindered N-alkoxyamines was very effective. Provides excellent flame retardancy. A further advantage of the present invention is improved mechanical properties due to the low loading level of flame retardant.

^a)発火した試験バーから滴下している燃焼滴下が、ＵＬ９４試験標準の試験バーの下に置かれた綿を発火する（５回の試験のうちの）試験回数 Table 3
Test Bar Properties and UL94V (1.6 mm) Results for Polypropylene Homopolymer Containing the Flame Retardant Composition of the Present Invention After Leaching at 70 ° C. for 7 Days in Deionized Water

^a) Combustion dripping from the ignited test bar ignites cotton placed under the UL 94 test standard test bar (of 5 tests)

It can be concluded from the results presented in Table 3 that the polymer composition of the present invention is characterized by its excellent leaching resistance to water. After the leaching test, it is observed that there is virtually no mass loss and no change in sample thickness. Example 4 of the present invention shows that a UL94V-0 ranking was obtained during the leaching test.

Table 4
Results of tests according to DIN 4102-B2 (flame size: 40 mm) obtained from 200 μm films of polypropylene homopolymer containing different flame retardant compositions

It can be concluded from the results reported in Table 4 that the polymer composition of the present invention exhibits improved flame retardancy compared to a reference composition containing a single additive at the same loading. . By using the composition of the present invention, both the burning time and the damaged length can be significantly reduced. In addition, Examples 9 and 10 of the present invention demonstrate that combustion dripping can be prevented by use of the flame retardant composition of the present invention.

Table 5
Results of tests according to DIN 4102-B2 (flame size: [RX1] 20 mm) obtained from 1.0 mm platelets of polypropylene homopolymer containing different flame retardant compositions

The results reported in Table 5 indicate that the polymer composition of the present invention exhibits superior flame retardancy with DIN 4102-B2 (1.0 mm). Although none of the reference compositions containing a single additive showed significant flame retardant behavior, the inventive combination of phosphonate and sterically hindered N-alkoxyamine is a very effective flame retardant. Provide sex. In addition, Example 12 of the present invention demonstrates that combustion dripping can be prevented by use of the flame retardant composition of the present invention.

^a)発火した試験バーから滴下している燃焼滴下が、ＵＬ９４試験標準の試験バーの下に置かれた綿を発火する（５回の試験のうちの）試験回数 Table 6
Results of UL94V (1.6 mm) test with PP block copolymers containing different flame retardant compositions

^a) Combustion dripping from the ignited test bar ignites cotton placed under the UL 94 test standard test bar (of 5 tests)

  It can be seen from the results described above that the compositions of the present invention are characterized by excellent flame retardancy and self-extinguishing properties.

Claims (10)

a) The following:
a ′) the following formula:

Of melamine phenylphosphonate and b ′)

A guanidine phenylphosphonate salt of the formula
R _{1 to} R ₅ represent hydrogen;
R _{6 to} R ₉ are independently of each other hydrogen or C ₁ -C ₄ alkyl, phenyl, phenyl-C ₁ -C ₄ alkyl, (C ₁ -C ₄ alkyl) _1-3 phenyl and (C ₁ -C ₄ alkyl) represents a substituent selected from the group consisting of _1-2 hydroxyphenyl; and x represents a number from 1.0 to 2.0.
A phenylphosphonate selected from the group consisting of:
b) 2,2,6,6-tetraalkylpiperidine-1-oxide, 1-hydroxy-2,2,6,6-tetraalkylpiperidine, 1-alkoxy-2,2,6,6-tetraalkylpiperidine, 1-acyloxy-2,2,6,6-piperidine, 1-hydroxy-2,2,6,6-tetraalkylpiperazine, 1-alkoxy-2,2,6,6-tetraalkylpiperazine and 1-acyloxy- A tetraalkylpiperidine or tetraalkylpiperazine derivative selected from the group consisting of 2,2,6,6-tetraalkylpiperazine;
c) A composition comprising a polyolefin homopolymer and a thermoplastic polymer selected from the group consisting of copolymers of olefins with each other or with vinyl monomers. a) The following:
a ′) the following formula:

Wherein x represents a number from 1.0 to 2.0; and b ') the following formula:

A phenylphosphonate selected from the group consisting of guanidine phenylphosphonates, wherein x represents a number from 1.0 to 2.0;
b) 2,2,6,6-tetraalkylpiperidine-1-oxide, 1-hydroxy-2,2,6,6-tetraalkylpiperidine, 1-alkoxy-2,2,6,6-tetraalkylpiperidine and A tetraalkylpiperidine derivative selected from the group consisting of 1-acyloxy-2,2,6,6-tetraalkylpiperidine;
The composition of claim 1 comprising c) a polyolefin homopolymer and a thermoplastic polymer selected from the group consisting of copolymers of olefins with each other or with vinyl monomers. a) phenylphosphonate (I ′) or (II ′);
b) a tetraalkylpiperidine derivative selected from the group consisting of 1-alkoxy-2,2,6,6-tetraalkylpiperidine and 1-acyloxy-2,2,6,6-tetraalkylpiperidine;
The composition of claim 2 comprising c) a polyolefin homopolymer and a thermoplastic polymer selected from the group consisting of copolymers of olefins with each other or with vinyl monomers. Following formula:

2,2,6,6-tetraalkylpiperidine-1-oxide of
Following formula:

Of 1-hydroxy-2,2,6,6-tetraalkylpiperidine,
Following formula:

1-alkoxy-2,2,6,6-tetraalkylpiperidine of
Following formula:

Of 1-acyloxy-2,2,6,6-tetraalkylpiperidine [wherein
One of R _a and R _b is
Represents hydrogen or N substituent, the other represents O substituent or C substituent, or R _a and R _b both represent hydrogen, O substituent or C substituent;
R is, C ₁ -C ₂₀ alkyl, C ₅ -C having ₆ cycloalkyl, or additional substituents, C ₂ -C ₂₀ represents alkyl, a C ₅ -C ₆ cycloalkyl or C ₂ -C ₂₀ alkenyl;
Ac represents an acyl group of C ₁ -C ₂₀ carboxylic acids;
R _{1 to} R ₄ each represent C _{1 to} C ₄ alkyl;
R ₅ and R _6, independently of one another, hydrogen or C ₁ -C ₄ alkyl, C ₁ -C ₃ alkylphenyl and Table carded a substituent selected from the group consisting of phenyl, or R ₅ and R ₆ Together, represents oxo)
The composition according to claim 1, comprising at least one tetraalkylpiperidine derivative selected from the group consisting of as component b). One of R _a and R _b is
Represents hydrogen or N substituent, the other represents O substituent or C substituent, or R _a and R _b both represent hydrogen, O substituent or C substituent;
R represents C ₁ -C ₈ alkyl, C ₅ -C ₆ cycloalkyl, or C ₂ -C ₈ alkyl, C ₅ -C ₆ cycloalkyl or C ₂ -C ₈ alkenyl with additional substituents;
Ac is an acyl group of C ₁ -C ₈ carboxylic acid;
R _{1 to} R ₄ are each methyl; and R ₅ and R ₆ each comprise at least one tetraalkylpiperidine derivative IIIa, IIIb, IIIc or IIId, each representing hydrogen, as component b). Composition. One of R _a and R _b is
Represents hydrogen or N substituent, the other represents O substituent or C substituent, or R _a and R _b both represent O substituent or C substituent;
R represents C ₁ -C ₈ alkyl, C ₅ -C ₆ cycloalkyl, or C ₂ -C ₈ alkyl, C ₅ -C ₆ cycloalkyl or C ₂ -C ₈ alkenyl, substituted with hydroxy;
Ac is an acyl group of C ₁ -C ₈ carboxylic acid;
R _{1 to} R ₄ are each methyl; and R ₅ and R ₆ each comprise at least one tetraalkylpiperidine derivative IIIa, IIIb, IIIc or IIId, each representing hydrogen, as component b). Composition. following:
1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine,
Bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino) -s-triazine,
Bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate,
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6-chloro-s-triazine,
1- (2-hydroxy-2-methylpropoxy) -4-hydroxy-2,2,6,6-tetramethylpiperidine,
1- (2-hydroxy-2-methylpropoxy) -4-oxo-2,2,6,6-tetramethylpiperidine,
1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,
Bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) sebacate,
Bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) adipate,
2,4-bis {N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] -N-butylamino} -6- (2- Hydroxyethylamino) -s-triazine,
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6-chloro-s-triazine and N, N'-bis (3-amino Propyl) ethylenediamine) reaction product,
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino) -s-triazine,
2,4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine) and 2-chloro-4,6-bis (dibutylamino) -s-triazine end-capped An oligomeric compound which is a condensate with 4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -s-triazine;
Following formula:

And the following formula:

7. A composition according to claim 6 comprising as component b) at least one tetraalkylpiperidine derivative IIIc or IIId selected from the group consisting of compounds wherein n is 1 to 15. a) phenylphosphonate (I ′) or (II ′);
b) The following:
1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine,
Bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino) -s-triazine,
Bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate,
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6-chloro-s-triazine,
1- (2-hydroxy-2-methylpropoxy) -4-hydroxy-2,2,6,6-tetramethylpiperidine,
1- (2-hydroxy-2-methylpropoxy) -4-oxo-2,2,6,6-tetramethylpiperidine,
1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,
Bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) sebacate,
Bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) adipate,
2,4-bis {N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] -N-butylamino} -6- (2- Hydroxyethylamino) -s-triazine,
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6-chloro-s-triazine and N, N'-bis (3-amino Propyl) ethylenediamine) reaction product,
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino) -s-triazine,
2,4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine) and 2-chloro-4,6-bis (dibutylamino) -s-triazine end-capped An oligomeric compound which is a condensate with 4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -s-triazine;
Following formula:

And the following formula:

At least one tetraalkylpiperidine derivative IIIc or IIId selected from the group consisting of compounds wherein n is 1 to 15;
8. A composition according to claim 2 or 7, comprising c) a polyolefin homopolymer and a thermoplastic polymer selected from the group consisting of copolymers of olefins with each other or with vinyl monomers. a) The following:
a ′) the following formula:

Of melamine phenylphosphonate and b ′)

Of guanidine phenylphosphonate [where:
R _{1 to} R ₅ represent hydrogen;
R _{6 to} R ₉ are independently of each other hydrogen or C ₁ -C ₄ alkyl, phenyl, phenyl-C ₁ -C ₄ alkyl, (C ₁ -C ₄ alkyl) _1-3 phenyl and (C ₁ -C ₄ alkyl) represents a substituent selected from the group consisting of _1-2 hydroxyphenyl; and x represents a number from 1.0 to 2.0.
A phenylphosphonate selected from the group consisting of:
b) 2,2,6,6-tetraalkylpiperidine-1-oxide, 1-hydroxy-2,2,6,6-tetraalkylpiperidine, 1-alkoxy-2,2,6,6-tetraalkylpiperidine and A tetraalkylpiperidine derivative selected from the group consisting of 1-acyloxy-2,2,6,6-tetraalkylpiperidine;
Containing the mixture.   A method of imparting flame retardancy to a thermoplastic polymer substrate, wherein the mixture of claim 9 is added to a thermoplastic polymer selected from the group consisting of polyolefin homopolymers and copolymers of olefins with each other or with vinyl monomers A method comprising: